Leuco polymers as bluing agents in laundry care compositions

ABSTRACT

A leuco polymer includes a leuco monomer and an alkene. The leuco polymer has a molecular weight of at least 500 and is obtainable by polymerization of the leuco monomer and one or more alkene co-monomers. The leuco monomer consists of an alkene covalently bound to a leuco moiety and the leuco monomer has a molar extinction coefficient at a wavelength in the range 400 to 750 nm of less than 1000 M−1cm−1. The alkene monomer(s) have a molar extinction coefficient at a wavelength in the range 400 to 750 nm that is less than 100 M−1cm−1. Methods of making the leuco polymer, laundry care compositions comprising the leuco polymer and methods of treating textiles with such laundry care compositions.

TECHNICAL FIELD

This application describes laundry care compositions that contain leucopolymers and their use in the laundering of textile articles. Thesetypes of leuco polymers are provided in a stable, substantiallycolorless state and then may be transformed to an intense colored stateupon exposure to certain physical or chemical changes such as, forexample, exposure to oxygen, ion addition, exposure to light, and thelike. The laundry care compositions containing the leuco polymers aredesigned to enhance the apparent or visually perceived whiteness of, orto impart a desired hue to, textile articles washed or otherwise treatedwith the laundry care composition.

BACKGROUND

As textile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. As such, to visually enhance these textilesubstrates and counteract the fading and yellowing the use of polymericcolorants for coloring consumer products has become well known in theprior art. For example, it is well known to use whitening agents, eitheroptical brighteners or blueing agents, in textile applications. However,traditional whitening agents when used at levels providing consumernoticeable whiteness benefits may either adversely impact finishedproduct aesthetics, or if highly depositing, have issues with build upover time and over hueing.

Leuco dyes are also known in the prior art to exhibit a change from acolorless or slightly colored state to a colored state upon exposure tospecific chemical or physical triggers. The change in coloration thatoccurs is typically visually perceptible to the human eye. All existingcompounds have some absorbance in the visible light region (400-750 nm),and thus more or less have some color. In this invention, a dye isconsidered as a “leuco dye” if it did not render a significant color atits application concentration and conditions, but renders a significantcolor in its triggered form. The color change upon triggering stems fromthe change of the molar attenuation coefficient (also known as molarextinction coefficient, molar absorption coefficient, and/or molarabsorptivity in some literatures) of the leuco dye molecule in the400-750 nm range, preferably in the 500-650 nm range, and mostpreferably in the 530-620 nm range. The increase of the molarattenuation coefficient of a leuco dye before and after the triggeringshould be bigger than 50%, more preferably bigger than 200%, and mostpreferably bigger than 500%.

As such, there remains a need for an effective whitening agent thatdeposits to provide the desired whiteness benefit yet does not adverselyimpact finished product aesthetics or cause over hueing after multiplewashes.

It has now surprisingly been found that the presently claimed leucopolymers provide the desired consumer whiteness benefit, without adverseeffects.

SUMMARY OF THE INVENTION

In a first embodiment, the invention provides a leuco polymer comprisinga leuco monomer and an alkene. The skilled artisan realizes that boththe leuco monomer alkene and the co-monomer alkene will be alkylenemoieties once incorporated into the leuco polymer. The leuco polymer hasa molecular weight of at least 500 and is obtainable by polymerizationof the leuco monomer and one or more alkene co-monomers. The leucomonomer comprising an alkene covalently bound to a leuco moiety and theleuco monomer has a molar extinction coefficient at a wavelength in therange 400 to 750 nm of less than 1000 M⁻¹cm⁻¹. The alkene monomer(s)have a molar extinction coefficient at a wavelength in the range 400 to750 nm that is less than 100 M⁻¹cm⁻¹.

In a second embodiment, the invention provides a laundry carecomposition comprising (a) laundry care ingredient, and (b) a leucopolymer. The leuco polymer includes a leuco monomer and an alkene. Theleuco polymer has a molecular weight of at least 500 and is obtainableby polymerization of the leuco monomer and one or more alkeneco-monomers. The leuco monomer consists of an alkene covalently bound toa leuco moiety and the leuco monomer has a molar extinction coefficientat a wavelength in the range 400 to 750 nm of less than 1000 M⁻¹cm⁻¹.The alkene monomer(s) have a molar extinction coefficient at awavelength in the range 400 to 750 nm that is less than 100 M⁻¹cm⁻¹.

In a third embodiment, the invention provides a method of treating atextile material, the method comprising the steps of (a) treating thetextile material with an aqueous solution of the leuco polymer, (b)optionally, rinsing the textile material, and (c) optionally, drying thetextile material.

DETAILED DESCRIPTION Definitions

As used herein, the term “alkoxy” is intended to include C₁-C8 alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the interchangeable terms “alkyleneoxy” and“oxyalkylene,” and the interchangeable terms “polyalkyleneoxy” and“polyoxyalkylene,” generally refer to molecular structures containingone or more than one, respectively, of the following repeating units:—C₂H₄O—, —C₃H₆O—, —C₄H₈O—, and any combinations thereof. Non-limitingstructures corresponding to these groups include —CH₂CH₂O—,—CH₂CH₂CH₂O—, —CH₂CH₂CH₂CH₂O—, —CH₂CH(CH₃)O—, and —CH₂CH(CH₂CH₃)O—, forexample. Furthermore, the polyoxyalkylene constituent may be selectedfrom the group consisting of one or more monomers selected from a C₂₋₂₀alkyleneoxy group, a glycidyl group, or mixtures thereof.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

As used herein, the terms “alkyl” and “alkyl capped” are intended tomean any univalent group formed by removing a hydrogen atom from asubstituted or unsubstituted hydrocarbon. Non-limiting examples includehydrocarbyl moieties which are branched or unbranched, substituted orunsubstituted including C₁-C₁₈ alkyl groups, and in one aspect, C₁-C₆alkyl groups.

As used herein, unless otherwise specified, the term “aryl” is intendedto include C₃-C₁₂ aryl groups. The term “aryl” refers to bothcarbocyclic and heterocyclic aryl groups.

As used herein, the term “alkaryl” refers to any alkyl-substituted arylsubstituents and aryl-substituted alkyl substituents. More specifically,the term is intended to refer to C₇₋₁₆ alkyl-substituted arylsubstituents and C₇₋₁₆ aryl substituted alkyl substituents which may ormay not comprise additional substituents.

As used herein, the term “detergent composition” is a sub-set of laundrycare composition and includes cleaning compositions including but notlimited to products for laundering fabrics. Such compositions may bepre-treatment composition for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and “stain-stick” or pre-treat types.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose,bar form and/or flake type washing agents and/or fabric treatmentcompositions, including but not limited to products for launderingfabrics, fabric softening compositions, fabric enhancing compositions,fabric freshening compositions, and other products for the care andmaintenance of fabrics, and combinations thereof. Such compositions maybe pre-treatment compositions for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and/or “stain-stick” or pre-treat compositions orsubstrate-laden products such as dryer added sheets.

As used herein, the term “leuco” (as used in reference to, for example,a compound, moiety, radical, dye, monomer, fragment, or polymer) refersto an entity (e.g., organic compound or portion thereof) that, uponexposure to specific chemical or physical triggers, undergoes one ormore chemical and/or physical changes that results in a shift from afirst color state (e.g., uncolored or substantially colorless) to asecond more highly colored state. Suitable chemical or physical triggersinclude, but are not limited to, oxidation, pH change, temperaturechange, and changes in electromagnetic radiation (e.g., light) exposure.Suitable chemical or physical changes that occur in the leuco entityinclude, but are not limited to, oxidation and non-oxidative changes,such as intramolecular cyclization. Thus, in one aspect, a suitableleuco entity can be a reversibly reduced form of a chromophore. In oneaspect, the leuco moiety preferably comprises at least a first and asecond π-system capable of being converted into a third combinedconjugated π-system incorporating said first and second π-systems uponexposure to one or more of the chemical and/or physical triggersdescribed above.

As used herein, the terms “leuco composition” or “leuco colorantcomposition” refers to a composition comprising at least two leucocompounds having independently selected structures as described infurther detail herein.

As used herein “average molecular weight” of the leuco colorant isreported as a weight average molecular weight, as determined by itsmolecular weight distribution: as a consequence of their manufacturingprocess, the leuco colorants disclosed herein may contain a distributionof repeating units in their polymeric moiety.

As used herein, the terms “maximum extinction coefficient” and “maximummolar extinction coefficient” are intended to describe the molarextinction coefficient at the wavelength of maximum absorption (alsoreferred to herein as the maximum wavelength), in the range of 400nanometers to 750 nanometers.

As used herein, the term “first color” is used to refer to the color ofthe laundry care composition before triggering, and is intended toinclude any color, including colorless and substantially colorless.

As used herein, the term “second color” is used to refer to the color ofthe laundry care composition after triggering, and is intended toinclude any color that is distinguishable, either through visualinspection or the use of analytical techniques such asspectrophotometric analysis, from the first color of the laundry carecomposition.

As used herein, the term “converting agent” refers to any oxidizingagent as known in the art other than molecular oxygen in any of itsknown forms (singlet and triplet states).

As used herein, the term “triggering agent” refers to a reactantsuitable for converting the leuco composition from a colorless orsubstantially colorless state to a colored state.

As used herein, the term “whitening agent” refers to a dye or a leucocolorant that may form a dye once triggered that when on white cottonprovides a hue to the cloth with a relative hue angle of 210 to 345, oreven a relative hue angle of 240 to 320, or even a relative hue angle of250 to 300 (e.g., 250 to 290).

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, articles such as “a” and “an” when used in a claim, areunderstood to mean one or more of what is claimed or described.

As used herein, the terms “include/s” and “including” are meant to benon-limiting.

As used herein, the term “solid” includes granular, powder, bar andtablet product forms.

As used herein, the term “fluid” includes liquid, gel, paste and gasproduct forms.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

In one aspect, the molar extinction coefficient of said second coloredstate at the maximum absorbance in the wavelength in the range 200 to1,000 nm (more preferably 400 to 750 nm) is preferably at least fivetimes, more preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the molar extinction coefficient of saidfirst color state at the wavelength of the maximum absorbance of thesecond colored state. Preferably, the molar extinction coefficient ofsaid second colored state at the maximum absorbance in the wavelength inthe range 200 to 1,000 nm (more preferably 400 to 750 nm) is at leastfive times, preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the maximum molar extinction coefficient ofsaid first color state in the corresponding wavelength range. Anordinarily skilled artisan will realize that these ratios may be muchhigher. For example, the first color state may have a maximum molarextinction coefficient in the wavelength range from 400 to 750 nm of aslittle as 10 M⁻¹cm⁻¹, and the second colored state may have a maximummolar extinction coefficient in the wavelength range from 400 to 750 nmof as much as 80,000 M⁻¹cm⁻¹ or more, in which case the ratio of theextinction coefficients would be 8,000:1 or more.

In one aspect, the maximum molar extinction coefficient of said firstcolor state at a wavelength in the range 400 to 750 nm is less than 1000M⁻¹cm⁻¹, and the maximum molar extinction coefficient of said secondcolored state at a wavelength in the range 400 to 750 nm is more than5,000 M⁻¹cm⁻¹, preferably more than 10,000, 25,000, 50,000 or even100,000 M⁻¹cm⁻¹. A skilled artisan will recognize and appreciate that apolymer comprising more than one leuco moiety may have a significantlyhigher maximum molar extinction coefficient in the first color state(e.g., due to the additive effect of a multiplicity of leuco moieties orthe presence of one or more leuco moieties converted to the secondcolored state). Where more than one leuco moiety is attached to amolecule, the maximum molar extinction coefficient of said second colorstate may be more than n×□ where n is the number of leuco moieties plusoxidized leuco moieties present on the molecule, and □ is selected from5,000 M⁻¹cm⁻¹, preferably more than 10,000, 25,000, 50,000 or even100,000 M⁻¹cm⁻¹. Thus for a molecule that has two leuco moieties, themaximum molar extinction coefficient of said second color state may bemore than 10,000 M⁻¹cm⁻¹, preferably more than 20,000, 50,000, 100,000or even 200,000 M⁻¹cm⁻¹. While n could theoretically be any integer, oneskilled in the art appreciates that n will typically be from 1 to 100,more preferably 1 to 50, 1 to 25, 1 to 10 or even 1 to 5.

In one preferred embodiment, the leuco entity upon conversion to thesecond more highly colored state provides to white substrates a colorwith a relative hue angle of 210 to 345, or even a relative hue angle of240 to 320, or even a relative hue angle of 250 to 300 (e.g., 250 to290). The relative hue angle can be determined by any suitable method asknown in the art. However, preferably it may be determined as describedin further detail herein with respect to deposition of the leuco entityon cotton relative to cotton absent any leuco entity.

The leuco polymer as presently claimed is obtainable by polymerizationof a leuco monomer and one or more alkene co-monomers.

The leuco monomer is an organic molecule which when dissolved in anorganic solvent has a maximum molar absorption extinction coefficient ofless than 1000 M⁻¹cm⁻¹, preferably less than 500 M⁻¹cm⁻¹, mostpreferably less than 250 M⁻¹cm⁻¹, and in its oxidized form has a maximummolar extinction coefficient of more than 1000 M⁻¹cm⁻¹, preferablygreater than 4000 M⁻¹cm⁻¹, more preferably greater than 15000 M⁻¹cm⁻¹,still more preferably more than 30,000 M⁻¹cm⁻¹, most preferably morethan 50,000 M⁻¹cm⁻¹ at a wavelength in the range 400-750 nm, preferably500-650 nm, most preferably 530-620 nm.

Molar absorption coefficients are preferably measured in an organicsolvent, preferably propan-2-ol, using a cell with a path length of 1, 5or 10 cm.

The leuco monomer may be uncharged, or may be either anionically orcationically charged in aqueous solution at a pH in the range from 6 to11. To qualify as charged in the present application, the leuco monomermust comprise a moiety with a pKa or pKb in the range from about 7.0 toabout 10.0. An uncharged leuco monomer may comprise no groups bearing acharge, or it may comprise groups that have opposite charges such thatthe charges sum to zero. An anionic leuco monomer may contain at leastone group selected from the group consisting of a sulfonic acid and acarboxylic acid. A cationic leuco monomer may contain at least onequaternary amine group.

When the leuco monomer is anionic, the dye monomer preferably has atleast one SO₃— and/or CO₂— group. The dye monomer may have more than oneSO₃— and/or CO₂— group. Preferably the dye monomer has one, two or threeSO₃— groups. When the leuco monomer is cationic, the cationic charge ismay be delocalized into at least one aromatic ring of the leuco monomer,and is preferably delocalized into more than one aromatic ring in theoxidized leuco form.

Preferably, the leuco monomer is of the form:

wherein Y is an organic bridging group covalently connecting a leucomoiety to the alkene moiety of the leuco monomer and R¹ is selected fromH, unsubstituted or substituted alkyl, unsubstituted or substitutedaryl, benzyl, halogen, ester, acid amide, and cyano.

Preferably, the organic bridging group is selected from —CON(R⁴)—,—CO₂—, —N(R⁴)—, —O—, —S—, —SO₂—, —SO₂N(R⁴)—, —N(COR⁴)—, and —N(SO₂R⁴)—;wherein R⁴ is selected from the group consisting of H, phenyl, benzyland unsubstituted or substituted C₁-C₆ branched or linear alkyl whereina divalent substituent of said linear or branched alkyl is locatedbetween a carbon atom and either a second carbon atom or a carbon atomand a hydrogen atom of said alkyl group and wherein said divalentsubstituent is selected from the group consisting of —O—, —S—, —SO₂—,—CO₂—, and an amine. Most preferably, the organic bridging group is—CON(R⁴)—. Preferably, R⁴ is selected: from: H and Me.

In one aspect, the Y group is bound directly to a carbon atom of anaromatic ring of the leuco moiety.

Preferably, R¹ is selected from: H; Me; Et; Pr; CO₂C₁-C₄ branched andlinear alkyl chains; phenyl; benzyl; CN; Cl; and, F. More preferably, R¹is selected from: H; and, Me.

Preferably, the leuco moiety is an organic group selected from leucodiarylmethane, leuco triarylmethane, leuco oxazine, leuco thiazine,leuco hydroquinone, and leuco arylaminophenol. Most preferred classesare leuco triarylmethane, leuco hydroquinone, and leuco arylaminophenol.

Suitable diarylmethane leuco moieties for use herein include, but arenot limited to, diarylmethylene derivatives capable of forming a secondcolored state as described herein. Suitable examples include, but arenot limited to, moieties derived from Michler's methane, adiarylmethylene substituted with an —OH group (e.g., Michler's hydrol)and ethers and esters thereof, a diarylmethylene substituted with aphotocleavable moiety, such as a —CN group(bis(para-N,N-dimethyl)phenyl)acetonitrile), and similar such compounds.

A preferred class per se are leuco triarylmethane. Suitable leucomonomers comprising triarylmethane leuco moieties include but are notlimited to those structures shown immediately below.

The leuco monomer may be further substituted by uncharged organic groupshaving a total molecular weight of less than 400. Preferred, unchargedorganic groups are selected from: NHCOCH₃; CH₃; C₂H₅; CH₃O; C₂H₅O;amine; Cl; F; Br; I; NO₂; CH₃SO₂; and, CN.

Most preferably the leuco monomer is formed by reaction of a leucocompound containing an NH₂ or OH group with acryloyl chloride(2-propenoyl chloride) or methacryloyl chloride (2-methylprop-2-enoylchloride). Most preferably the leuco monomer is of the formleuco-N—H—C(O)—CH═CH₂, leuco-NH—C—(O)—C(Me)═CH₂, leuco-O—C(O)—CH═CH₂, orleuco-O—C—(O)—C(Me)═CH₂.

An alternative preferred route to form a leuco monomer is via reactionof the amine groups of a leuco compound with an alkene bearing a pendantepoxide group. For example:

The alkene co-monomer may be selected from any suitable alkene. Theco-monomer is preferably of the form:

wherein R² and R³ are independently selected from: H, C₁-C₈ branched,cyclic and linear alkyl chains, C(O)OH, CO₂C₁-C₁₈ branched and linearalkyl chains, —C(O)N (C₁-C₁₈)₂; —C(O)N(C₁-C₁₈)H; —C(O)NH₂;heteroaromatic, phenyl, benzyl, polyether, cyano, Cl and F. Where C₁-C₁₈is specified a preferred range is C₁ to C₄.

The R² and R³ of the co-monomer may be further substituted by chargedand uncharged organic groups having a total molecular weight of lessthan 400. Preferred uncharged organic groups are selected from: NHCOCH₃,CH₃, C₂H₅, OH, CH3O, C2H5O, amine, Cl, F, Br, I, NO₂, CH₃SO₂, and CN.

The phenyl, benzyl and alkyl chains may be substituted by furtherorganic groups selected from: OH; F; Cl; alkoxy (preferably OCH₃), SO₃—,CO₂H, amine, quaternary amine, acid amide and ester. When phenyl orbenzyl groups are present, the aromatic is not substituted by OH.

Where the alkyl has not been specified, C₁ to C₄ branched or linear ispreferred.

Examples of suitable co-monomers include but are not limited to methylacrylate, ethyl acrylate, butyl acrylate, t-butyl acrylate, benzylmethacrylate, methyl methacrylate, ethyl methacrylate, butylmethacrylate, t-butyl methacrylate, styrene, 2-vinyl pyridine, 4-vinylphenol, 9-vinyl-9H-carbazole,4,4-dimethyl-2-(prop-1-ene-2-yl)-oxazol-5(4H)-one, vinyl acetate,acrylonitrile, 4,4-dimethyl-2-vinyloxazol-5(4H)-one, glycidylmethacrylate, stearyl methacrylate, poly(ethylene glycol) ethyl ethermethacrylate, poly(ethylene glycol) methyl ether methacrylate,2-hydroxypropyl methacrylate, 4-pentenoic acid, ethyl-2-cyanoacrylate,di(ethylene glycol) methyl ether methacrylate, isopropyl methacrylate,glycosyloxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate,3-chloro-2-hydroxypropyl methacrylate, 2-ethylhexyl methacrylatee,2(methylthio)ethyl methacrylate, cyclohexyl methacrylate, hexylmethacrylate, 2-isocyanatoethyl methacrylate, furfuryl methacrylate,tetrahydrofurfuryl methacrylate, 2-acrylamido-2-methyl-1-propanesulfonicacid, N-(3-aminophenyl)acrylamide, 2-(tert-butylamino)ethylmethacrylate, N-(6-aminopyridin-2-yl)acrylate, 4-vinylphenylboronicacid, 2-butoxyethyl methacryate, and 2-acrylamidopyridine. Preferredco-monomers include but are not limited to N,N-dimethylaminoethylmethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate,acrylamide, sodium 4-vinylbenzene sulfonate, N,N-diethylaminoethylmethacrylate, acrylic acid, sodium acrylic acid, methacrylic acid,sodium methacrylic acid, vinyl pyrrolidone, maleic anhydride,2-aminoethyl methacrylate hydrochloride, 2-aminoethyl methacrylatehydrochloride, N,N-dimethylacrylamide, N-isopropylacrylamide, potassium5-methyl-4-oxohex-5-ene-1-sulfonate, itaconic acid, potassium3-sulfopropyl methacrylate, 2-(dimethylamino)ethyl methacrylamide,4-vinylbenzoic acid, vinyl methyl ether, 2-aminoethyl methacrylate, and4-ethenyl-N,N′-di(C₁-C₄)alkylbenzenecarboximidamide.

Mixtures of co-monomers may be used. It is preferred that the >50 wt %,more preferably >80 wt %, of the comonomers are selected fromco-monomers that have a molecular weight of less than 300 and containsan amine, amide, OH, OCH₃, SO₃— or COO— group. Most preferably, theco-monomers contain an amine or OCH₃ group.

Most preferably >50 wt %, preferably >80 wt %, of the co-monomers areacrylates with pendant tertiary amine groups, most preferably selectedfrom N,N-dimethylaminoethyl methacrylate and N,N-diethylaminoethylmethacrylate.

Additional co-monomers may be added to the polymer which are covalentlybound to radical photobleaches such as vitamin K3 or 2-ethylanthraquinone. Other organic active ingredients such as sunscreens,antifungal agents, bleach catalysts, antimicrobial, antiwrinkle may alsobe covalently linked to the polymer. Examples of such ingredients are5-chloro-2-(2,4-dichlorophenoxy)phenol,6-acetoxy-2,4-dimethyl-m-dioxane, para-aminobenzoic acid,diethanolaminep-methoxy cinnamate and oxybenzone. Most preferably theingredient contains an NH₂ group and the monomer is created in ananalogous manner to the leuco monomer. These are preferably present at alower level than the leuco monomer.

The leuco polymer is obtained (formed) by polymerization of the integers(a) leuco monomer and (b) alkene co-monomer as detailed above. The leucopolymer may be derived from a mixture of different leuco monomers, forexample carrying different leuco moieties, and may also incorporate morethan one alkene co-monomer. Preferably, the leuco polymer has asolubility of greater than 1 mg/L in a 1 g/L sodium dodecyl sulfateaqueous solution at pH=7.

Preferably the leuco polymer gives a hue to the cloth with a relativehue angle of 210 to 345, or even a relative hue angle of 240 to 320, oreven a relative hue angle of 250 to 300 (e.g., 250 to 290). The relativehue angle can be determined by any suitable method as known in the art.However, preferably it may be determined as described in further detailherein with respect to deposition of the leuco entity on cotton relativeto cotton absent any leuco entity.

The polymer is obtainable by co-polymerization of the dye monomer withsuitable unsaturated organic co-monomers. Preferably the polymercontains 0.1 to 30 mole % leuco monomer units, more preferably 1 to 15mole % leuco monomers units, most preferably 2 to 10 mole % leucomonomer units.

Preferably the polymer contains less than 20 mole %, more preferablyless than 5 mole % of co-monomers bearing CO₂— or SO₃— groups.

The monomers within the polymer may be arranged in any suitable manner.For example as alternating copolymers possessing regularly alternatingmonomer residues; periodic copolymers having monomer residue typesarranged in a repeating sequence; random copolymers having a randomsequence of monomer residue types; statistical copolymers having monomerresidues arranged according to a known statistical rule; blockcopolymers having two or more homopolymer subunits linked by covalentbonds. Most preferably the polymer is a random copolymer. The polymershould have a molecular weight 500 and greater, preferably 2000 andgreater, preferably 5000 and greater. In this context the molecularweight is the number average molecular weight. This is the ordinaryarithmetic mean of the molecular weights of the individualmacromolecules. It is determined by measuring the molecular weight of jpolymer molecules, summing the weights, and dividing by j. Molecularweights are determined by Gel Permeation Chromatography.

The leuco polymer may have a solubility of greater than 10 mg/L in a 1g/L sodium dodecyl sulfate solution at pH=7.

Water solubility is enhanced by the presence of hydroxy, amino andcharged groups in the polymer, preferably anionic charged groups.Preferably the polymer is of the form:

wherein a and b are integers each greater than or equal to 1 andX=Y-Leuco.

Preferably, the index a is greater than the index b (a>b). Morepreferably the ratio a:b is from 99.9:0.1 to 70:30.

It is preferred that the dye-polymer has a number average molecularweight in the range from 500 to 500000, preferably from 2000 to 100000,more preferably 5000 to 50000.

The present invention relates to a class of leuco colorants that may beuseful for use in laundry care compositions, such as liquid laundrydetergent, to provide a hue to whiten textile substrates. Leucocolorants are compounds that are essentially colorless or only lightlycolored but are capable of developing an intense color upon activation.One advantage of using leuco compounds in laundry care compositions isthat such compounds, being colorless until activated, allow the laundrycare composition to exhibit its own color. The leuco colorant generallydoes not alter the primary color of the laundry care composition. Thus,manufacturers of such compositions can formulate a color that is mostattractive to consumers without concern for added ingredients, such asbluing agents, affecting the final color value of the composition.

The leuco moiety covalently bound to the alkene monomer can be anysuitable leuco moiety. Suitable leuco moieties include, but are notlimited to, diarylmethane moieties, triarylmethane moieties, oxazinemoieties, thiazine moieties, hydroquinone moieties, and arylaminophenolmoieties. In a more particular aspect, the leuco moiety is a univalentor polyvalent moiety derived by removal of one or more hydrogen atomsfrom a structure of Formula (I), (II), (III), (IV), or (V) describedbelow:

wherein the ratio of Formula I-V to its oxidized form is at least 1:19,1:9, or 1:3, preferably at least 1:1, more preferably at least 3:1, mostpreferably at least 9:1 or even 19:1.

In the structure of Formula (I), each individual R_(o), R_(m) and R_(p)group on each of rings A, B and C is independently selected from thegroup consisting of hydrogen, deuterium and R⁵; each R⁵ is independentlyselected from the group consisting of halogens, nitro, alkyl,substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,—(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻,—C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹,—S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR²,—NR¹C(O)NR²R³, —OR¹, —NR¹R², —P(O)₂R¹, —P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and—P(O)(O⁻)₂, wherein the index n is an integer from 0 to 4, preferablyfrom 0 to 1, most preferably 0; wherein two R_(o) on different A, B andC rings may combine to form a fused ring of five or more members; whenthe fused ring is six or more members, two R_(o) on different A, B and Crings may combine to form an organic linker optionally containing one ormore heteroatoms; in one embodiment two R_(o) on different A, B and Crings combine to form a heteroatom bridge selected from —O— and —S—creating a six member fused ring; an R_(o) and R_(m) on the same ring oran R_(m) and R_(p) on the same ring may combine to form a fusedaliphatic ring or fused aromatic ring either of which may containheteroatoms; on at least one of the three rings A, B or C, preferably atleast two, more preferably at least three, most preferably all four ofthe R_(o) and R_(m) groups are hydrogen, preferably all four R_(o) andR_(m) groups on at least two of the rings A, B and C are hydrogen; insome embodiments, all R_(o) and R_(m) groups on rings A, B and C arehydrogen; preferably each R_(p) is independently selected from hydrogen,—OR¹ and —NR¹R²; no more than two, preferably no more than one of R_(p)is hydrogen, preferably none are hydrogen; more preferably at least one,preferably two, most preferably all three R_(p) are —NR¹R²; in someembodiments, one or even two of the Rings A, B and C may be replacedwith an independently selected C₃-C₉ heteroaryl ring comprising one ortwo heteroatoms independently selected from O, S and N, optionallysubstituted with one or more independently selected R⁵ groups; G isindependently selected from the group consisting of hydrogen, deuterium,C₁-C₁₆ alkoxide, phenoxide, bisphenoxide, nitrite, nitrile, alkyl amine,imidazole, arylamine, polyalkylene oxide, halides, alkylsulfide, arylsulfide, or phosphine oxide; in one aspect the fraction[(deuterium)/(deuterium+hydrogen)] for G is at least 0.20, preferably atleast 0.40, even more preferably at least 0.50 and most preferably atleast 0.60 or even at least 0.80;

wherein any two of R¹, R² and R³ attached to the same heteroatom cancombine to form a ring of five or more members optionally comprising oneor more additional heteroatoms selected from the group consisting of—O—, —NR¹⁵—, and —S—.

In the structure of Formula (II)-(III), e and f are independentlyintegers from 0 to 4; each R²⁰ and R²¹ is independently selected fromthe group consisting of halogens, a nitro group, alkyl groups,substituted alkyl groups, —NC(O)OR¹, —NC(O)SR¹, —OR¹, and —NR¹R²; eachR²⁵ is independently selected from the group consisting ofmonosaccharide moiety, disaccharide moiety, oligosaccharide moiety, andpolysaccharide moiety, —C(O)R¹, —C(O)OR¹, —C(O)NR¹R²; and each R²² andR²³ is independently selected from the group consisting of hydrogen,alkyl groups, and substituted alkyl groups.

In the structure of Formula (IV), R³⁰ is positioned ortho or para to thebridging amine moiety and is selected from the group consisting of —OR³⁸and —NR³⁶R³⁷, each R³⁶ and R³⁷ is independently selected from the groupconsisting of hydrogen, alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, acyl groups, R⁴, —C(O)OR¹, —C(O)R¹, and—C(O)NR¹R²; R³⁸ is selected from the group consisting of hydrogen, acylgroups, —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; g and h are independentlyintegers from 0 to 4; each R³¹ and R³² is independently selected fromthe group consisting of alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, alkaryl, substituted alkaryl,—(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻,—C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹,—S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR²,—NR¹C(O)NR²R³, —OR¹, —NR¹R², —P(O)₂R¹, —P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and—P(O)(O⁻)₂, wherein the index n is an integer from 0 to 4, preferablyfrom 0 to 1, most preferably 0; —NR³⁴R³⁵ is positioned ortho or para tothe bridging amine moiety and R³⁴ and R³⁵ are independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, and R⁴; R³³ isindependently selected from the group consisting of hydrogen, —S(O)₂R¹,—C(O)N(H)R¹; —C(O)OR¹; and —C(O)R¹; when g is 2 to 4, any two adjacentR³¹ groups may combine to form a fused ring of five or more memberswherein no more than two of the atoms in the fused ring may be nitrogenatoms.

In the structure of Formula (V), X⁴⁰ is selected from the groupconsisting of an oxygen atom, a sulfur atom, and NR⁴⁵; R⁴⁵ isindependently selected from the group consisting of hydrogen, deuterium,alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substitutedalkaryl, —S(O)₂OH, —S(O)₂O⁻, —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; R⁴⁰ andR⁴¹ are independently selected from the group consisting of—(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R², wherein the index n is an integerfrom 0 to 4, preferably from 0 to 1, most preferably 0; j and k areindependently integers from 0 to 3; R⁴² and R⁴³ are independentlyselected from the group consisting of alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, —S(O)₂R¹, —C(O)NR¹R²,—NC(O)OR¹, —NC(O)SR¹, —C(O)OR¹, —C(O)R¹, —(CH₂)_(n)—O—R¹, —(CH₂),—NR¹R²,wherein the index n is an integer from 0 to 4, preferably from 0 to 1,most preferably 0; R⁴⁴ is —C(O)R¹, —C(O)NR¹R², and —C(O)OR¹.

In the structures of Formula (I)-(V), wherein any charge present in anyof the proceeding groups is balanced with a suitable independentlyselected internal or external counterion. Suitable independentlyselected external counterions may be cationic or anionic. Examples ofsuitable cations include but are not limited to one or more metalspreferably selected from Group I and Group II, the most preferred ofthese being Na, K, Mg, and Ca, or an organic cation such as iminium,ammonium, and phosphonium. Examples of suitable anions include but arenot limited to: fluoride, chloride, bromide, iodide, perchlorate,hydrogen sulfate, sulfate, aminosulfate, nitrate, dihydrogen phosphate,hydrogen phosphate, phosphate, bicarbonate, carbonate, methosulfate,ethosulfate, cyanate, thiocyanate, tetrachlorozincate, borate,tetrafluoroborate, acetate, chloroacetate, cyanoacetate, hydroxyacetate,aminoacetate, methylaminoacetate, di- and tri-chloroacetate,2-chloro-propionate, 2-hydroxypropionate, glycolate, thioglycolate,thioacetate, phenoxyacetate, trimethylacetate, valerate, palmitate,acrylate, oxalate, malonate, crotonate, succinate, citrate,methylene-bis-thioglycolate, ethylene-bis-iminoacetate,nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate,chlorobenzoate, dichlorobenzoate, hydroxybenzo ate, aminobenzoate,phthalate, terephthalate, indolylacetate, chlorobenzenesulfonate,benzenesulfonate, toluenesulfonate, biphenyl-sulfonate andchlorotoluenesulfonate. Those of ordinary skill in the art are wellaware of different counterions which can be used in place of thoselisted above.

In the structures of Formula (I)-(V), R¹, R², R³, and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,and R⁴; wherein R⁴ is an organic group composed of one or more organicmonomers with said monomer molecular weights ranging from 28 to 500,preferably 43 to 350, even more preferably 43 to 250, wherein theorganic group may be substituted with one or more additional leucocolorant moieties conforming to the structure of Formula I-V. In oneaspect, R⁴ is selected from the group consisting of alkyleneoxy(polyether), oxoalkyleneoxy (polyesters), oxoalkyleneamine (polyamides),epichlorohydrin, quaternized epichlorohydrin, alkyleneamine,hydroxyalkylene, acyloxyalkylene, carboxyalkylene, carboalkoxyalkylene,and sugar. Where any leuco colorant comprises an R⁴ group with three ormore contiguous monomers, that leuco colorant is defined herein as a“polymeric leuco colorant”. One skilled in the art knows that theproperties of a compound with regard to any of a number ofcharacteristic attributes such as solubility, partitioning, deposition,removal, staining, etc., are related to the placement, identity andnumber of such contiguous monomers incorporated therein. The skilledartisan can therefore adjust the placement, identity and number of suchcontiguous monomers to alter any particular attribute in a more or lesspredictable fashion.

The leuco polymer present in the laundry care composition can be any ofthe leuco polymers described above in connection with the earlierembodiments of the invention. The leuco polymer can be present in thelaundry care composition in any suitable amount. In one aspect, thelaundry care composition comprises from about 0.001 wt.% to about 2.0wt.%, preferably about 0.05 wt.% to about 0.2 wt.%, of the leucopolymer. In such an embodiment, the laundry care composition cancomprise from about 2 wt.% to about 70 wt.% of surfactant (either asingle surfactant or, more preferably, a combination of surfactantsselected from those discussed below).

Laundry Care Ingredients Surfactant System

The products of the present invention may comprise from about 0.00 wt %,more typically from about 0.10 to 80% by weight of a surfactant. In oneaspect, such compositions may comprise from about 5% to 50% by weight ofsurfactant. Surfactants utilized can be of the anionic, nonionic,amphoteric, ampholytic, zwitterionic, or cationic type or can comprisecompatible mixtures of these types. Anionic and nonionic surfactants aretypically employed if the fabric care product is a laundry detergent. Onthe other hand, cationic surfactants are typically employed if thefabric care product is a fabric softener.

Anionic Surfactant

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,“soaps”, are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodium, potassium, ammonium, andalkylolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, or even from about 12 to about 18 carbon atoms.Soaps can be made by direct saponification of fats and oils or by theneutralization of free fatty acids. Particularly useful are the sodiumand potassium salts of the mixtures of fatty acids derived from coconutoil and tallow, i.e., sodium or potassium tallow and coconut soap.

Preferred alkyl sulphates are C8-18 alkyl alkoxylated sulphates,preferably a C12-15 alkyl or hydroxyalkyl alkoxylated sulphates.Preferably the alkoxylating group is an ethoxylating group. Typicallythe alkyl alkoxylated sulphate has an average degree of alkoxylationfrom 0.5 to 30 or 20, or from 0.5 to 10. The alkyl group may be branchedor linear. The alkoxylated alkyl sulfate surfactant may be a mixture ofalkoxylated alkyl sulfates, the mixture having an average (arithmeticmean) carbon chain length within the range of about 12 to about 30carbon atoms, or an average carbon chain length of about 12 to about 15carbon atoms, and an average (arithmetic mean) degree of alkoxylation offrom about 1 mol to about 4 mols of ethylene oxide, propylene oxide, ormixtures thereof, or an average (arithmetic mean) degree of alkoxylationof about 1.8 mols of ethylene oxide, propylene oxide, or mixturesthereof. The alkoxylated alkyl sulfate surfactant may have a carbonchain length from about 10 carbon atoms to about 18 carbon atoms, and adegree of alkoxylation of from about 0.1 to about 6 mols of ethyleneoxide, propylene oxide, or mixtures thereof. The alkoxylated alkylsulfate may be alkoxylated with ethylene oxide, propylene oxide, ormixtures thereof. Alkyl ether sulfate surfactants may contain a peakedethoxylate distribution. Specific example include C12-C15 EO 2.5Sulfate, C14-C15 EO 2.5 Sulfate and C12-C15 EO 1.5 Sulfate derived fromNEODOL® alcohols from Shell and C12-C14 EO3 Sulfate, C12-C16 EO3Sulfate, C12-C14 EO2 Sulfate and C12-C14 EO1 Sulfate derived fromnatural alcohols from Huntsman. The AES may be linear, branched, orcombinations thereof. The alkyl group may be derived from synthetic ornatural alcohols such as those supplied by the tradename Neodol® byShell, Safol®, Lial®, and Isalchem® by Sasol or midcut alcohols derivedfrom vegetable oils such as coconut and palm kernel. Another suitableanionic detersive surfactant is alkyl ether carboxylate, comprising aC10-C26 linear or branched, preferably C10-C20 linear, most preferablyC16-C18 linear alkyl alcohol and from 2 to 20, preferably 7 to 13, morepreferably 8 to 12, most preferably 9.5 to 10.5 ethoxylates. The acidform or salt form, such as sodium or ammonium salt, may be used, and thealkyl chain may contain one cis or trans double bond. Alkyl ethercarboxylic acids are available from Kao (Akypo®), Huntsman (Empicol®)and Clariant (Emulsogen®).

Other useful anionic surfactants can include the alkali metal salts ofalkyl benzene sulfonates, in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain (linear) or branched chainconfiguration. In some examples, the alkyl group is linear. Such linearalkylbenzene sulfonates are known as “LAS.” In other examples, thelinear alkylbenzene sulfonate may have an average number of carbon atomsin the alkyl group of from about 11 to 14. In a specific example, thelinear straight chain alkylbenzene sulfonates may have an average numberof carbon atoms in the alkyl group of about 11.8 carbon atoms, which maybe abbreviated as C11.8 LAS. Preferred sulphonates are C10-13 alkylbenzene sulphonate. Suitable alkyl benzene sulphonate (LAS) may beobtained, by sulphonating commercially available linear alkyl benzene(LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied bySasol under the tradename Isochem® or those supplied by Petresa underthe tradename Petrelab®, other suitable LAB include high 2-phenyl LAB,such as those supplied by Sasol under the tradename Hyblene®. A suitableanionic detersive surfactant is alkyl benzene sulphonate that isobtained by DETAL catalyzed process, although other synthesis routes,such as HF, may also be suitable. In one aspect a magnesium salt of LASis used. Suitable anionic sulfonate surfactants for use herein includewater-soluble salts of C8-C18 alkyl or hydroxyalkyl sulfonates; C11-C18alkyl benzene sulfonates (LAS), modified alkylbenzene sulfonate (MLAS)as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; methylester sulfonate (MES); and alpha-olefin sulfonate (AOS). Those alsoinclude the paraffin sulfonates may be monosulfonates and/ordisulfonates, obtained by sulfonating paraffins of 10 to 20 carbonatoms. The sulfonate surfactant may also include the alkyl glycerylsulfonate surfactants.

Anionic surfactants of the present invention may exist in an acid form,and said acid form may be neutralized to form a surfactant salt which isdesirable for use in the present detergent compositions. Typical agentsfor neutralization include the metal counterion base such as hydroxides,e.g., NaOH or KOH. Further preferred agents for neutralizing anionicsurfactants of the present invention and adjunct anionic surfactants orcosurfactants in their acid forms include ammonia, amines, oralkanolamines. Alkanolamines are preferred. Suitable non-limitingexamples including monoethanolamine, diethanolamine, triethanolamine,and other linear or branched alkanolamines known in the art; forexample, highly preferred alkanolamines include 2-amino-1-prop anol,1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol.

Nonionic Surfactant

Preferably the composition comprises a nonionic detersive surfactant.Suitable nonionic surfactants include alkoxylated fatty alcohols. Thenonionic surfactant may be selected from ethoxylated alcohols andethoxylated alkyl phenols of the formula R(OC2H4),OH, wherein R isselected from the group consisting of aliphatic hydrocarbon radicalscontaining from about 8 to about 15 carbon atoms and alkyl phenylradicals in which the alkyl groups contain from about 8 to about 12carbon atoms, and the average value of n is from about 5 to about 15.Other non-limiting examples of nonionic surfactants useful hereininclude: C8-C18 alkyl ethoxylates, such as, NEODOL® nonionic surfactantsfrom Shell; C6-C12 alkyl phenol alkoxylates where the alkoxylate unitsmay be ethyleneoxy units, propyleneoxy units, or a mixture thereof;C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers such as Pluronic® from BASF;C14-C22 mid-chain branched alcohols, BA; C14-C22 mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x is from 1 to 30;alkylpolysaccharides; specifically alkylpolyglycosides; polyhydroxyfatty acid amides; and ether capped poly(oxyalkylated) alcoholsurfactants. Specific example include C12-C15 EO7 and C14-C15 EO7NEODOL® nonionic surfactants from Shell, C12-C14 EO7 and C12-C14 EO9Surfonic® nonionic surfactants from Huntsman.

Highly preferred nonionic surfactants are the condensation products ofGuerbet alcohols with from 2 to 18 moles, preferably 2 to 15, morepreferably 5-9 of ethylene oxide per mole of alcohol. Suitable nonionicsurfactants include those with the trade name Lutensol® from BASF.Lutensol XP-50 is a Guerbet ethoxylate that contains an average of about5 ethoxy groups. Lutensol XP-80 and containing an average of about 8ethoxy groups. Other suitable non-ionic surfactants for use hereininclude fatty alcohol polyglycol ethers, alkylpolyglucosides and fattyacid glucamides, alkylpolyglucosides based on Guerbet alcohols.

Amphoteric Surfactant

The surfactant system may include amphoteric surfactant, such as amineoxide. Preferred amine oxides are alkyl dimethyl amine oxide or alkylamido propyl dimethyl amine oxide, more preferably alkyl dimethyl amineoxide and especially coco dimethyl amino oxide. Amine oxide may have alinear or mid-branched alkyl moiety.

Ampholytic Surfactants

The surfactant system may comprise an ampholytic surfactant. Specific,non-limiting examples of ampholytic surfactants include: aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents may contain at least about 8 carbon atoms, for example fromabout 8 to about 18 carbon atoms, and at least one contains an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 at column 19, lines 18-35, for suitable examples ofampholytic surfactants.

Zwitterionic Surfactant

Zwitterionic surfactants are known in the art, and generally includesurfactants which are neutrally charged overall, but carry at least onepositive charged atom/group and at least one negatively chargedatom/group. Examples of zwitterionic surfactants include: derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678at column 19, line 38 through column 22, line 48, for examples ofzwitterionic surfactants; betaines, including alkyl dimethyl betaine andcocodimethyl amidopropyl betaine, C₈ to C₁₈ (for example from C₁₂ toC₁₈) amine oxides and sulfo and hydroxy betaines, such asN-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl group canbe C₈ to C₁₈ and in certain embodiments from C₁₀ to C₁₄. A preferredzwitterionic surfactant for use in the present invention is thecocoamidopropyl betaine.

Cationic Surfactants

Examples of cationic surfactants include quaternary ammoniumsurfactants, which can have up to 26 carbon atoms specific. Additionalexamples include a) alkoxylate quaternary ammonium (AQA) surfactants asdiscussed in U.S. Pat. No. 6,136,769; b) dimethyl hydroxyethylquaternary ammonium as discussed in U.S. Pat. No. 6,004,922; c)polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003,WO 98/35004, WO 98/35005, and WO 98/35006, which is herein incorporatedby reference; d) cationic ester surfactants as discussed in U.S. Pat.Nos. 4,228,042, 4,239,660 4,260,529 and U.S. Pat. No. 6,022,844, whichis herein incorporated by reference; and e) amino surfactants asdiscussed in U.S. Pat. No. 6,221,825 and WO 00/47708, which is hereinincorporated by reference, and specifically amido propyldimethyl amine(APA). Useful cationic surfactants also include those described in U.S.Pat. No. 4,222,905, Cockrell, issued Sep. 16, 1980, and in U.S. Pat. No.4,239,659, Murphy, issued Dec. 16, 1980, both of which are alsoincorporated herein by reference. Quaternary ammonium compounds may bepresent in fabric enhancer compositions, such as fabric softeners, andcomprise quaternary ammonium cations that are positively chargedpolyatomic ions of the structure NR₄ ⁺, where R is an alkyl group or anaryl group.

Adjunct Cleaning Additives

The cleaning compositions of the invention may also contain adjunctcleaning additives. The precise nature of the cleaning adjunct additivesand levels of incorporation thereof will depend on the physical form ofthe cleaning composition, and the precise nature of the cleaningoperation for which it is to be used.

The adjunct cleaning additives may be selected from the group consistingof builders, structurants or thickeners, clay soilremoval/anti-redeposition agents, polymeric soil release agents,polymeric dispersing agents, polymeric grease cleaning agents, enzymes,enzyme stabilizing systems, bleaching compounds, bleaching agents,bleach activators, bleach catalysts, brighteners, dyes, hueing agents,dye transfer inhibiting agents, chelating agents, suds supressors,softeners, and perfumes. This listing of adjunct cleaning additives isexemplary only, and not by way of limitation of the types of adjunctcleaning additives which can be used. In principle, any adjunct cleaningadditive known in the art may be used in the instant invention.

Polymers

The composition may comprise one or more polymers. Non-limitingexamples, all of which may be optionally modified, includepolyethyleneimines, carboxymethylcellulose, poly(vinyl-pyrrolidone),poly (ethylene glycol), poly(vinyl alcohol),poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates oralkoxylated substituted phenols (ASP). as described in WO 2016/041676.An example of ASP dispersants, include but are not limited to, HOSTAPALBV CONC S1000 available from Clariant.

Polyamines may be used for grease, particulate removal or stain removal.A wide variety of amines and polyaklyeneimines can be alkoxylated tovarious degrees to achieve hydrophobic or hydrophilic cleaning. Suchcompounds may include, but are not limited to, ethoxylatedpolyethyleneimine, ethoxylated hexamethylene diamine, and sulfatedversions thereof. Useful examples of such polymers are HP20 availablefrom BASF or a polymer having the following general structure:

bis((C₂H₅O)(C₂H₄O)_(n))(CH₃)—N+-C_(x)H_(2x)—N+-(CH₃)-bis((C₂H₅O)(C₂H₄O)_(n)),wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or sulphonatedvariants thereof. Polypropoxylated-polyethoxylated amphiphilicpolyethyleneimine derivatives may also be included to achieve greatergrease removal and emulsification. These may comprise alkoxylatedpolyalkylenimines, preferably having an inner polyethylene oxide blockand an outer polypropylene oxide block. Detergent compositions may alsocontain unmodified polyethyleneimines useful for enhanced beverage stainremoval. PEI's of various molecular weights are commercially availablefrom the BASF Corporation under the trade name Lupasol® Examples ofsuitable PEI's include, but are not limited to, Lupasol FG®, LupasolG-35®.

The composition may comprise one or more carboxylate polymers, such as amaleate/acrylate random copolymer or polyacrylate homopolymer useful aspolymeric dispersing agents. Alkoxylated polycarboxylates such as thoseprepared from polyacrylates are also useful to provide clay dispersancy.Such materials are described in WO 91/08281. Chemically, these materialscomprise polyacrylates having one ethoxy side-chain per every 7-8acrylate units. The side-chains are of the formula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. The side-chains are esteror ether-linked to the polyacrylate “backbone” to provide a “comb”polymer type structure.

Preferred amphiphilic graft co-polymer(s) comprise (i) polyethyeleneglycol backbone; and (ii) at least one pendant moiety selected frompolyvinyl acetate, polyvinyl alcohol and mixtures thereof. An example ofan amphiphilic graft co-polymer is Sokalan HP22, supplied from BASF.

Alkoxylated substituted phenols as described in WO 2016/041676 are alsosuitable examples of polymers that provide clay dispersancy. Hostapal BVConc S1000, available from Clariant, is one non-limiting example of anASP dispersant.

Preferably the composition comprises one or more soil release polymers.Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN260 SRN300 and SRN325 supplied by Clariant. Other suitable soilrelease polymers are Marloquest polymers, such as Marloquest SL, HSCB,L235M, B, G82 supplied by Sasol. Other suitable soil release polymersinclude methyl-capped ethoxylated propoxylated soil release polymers asdescribed in U.S. Pat. No. 9,365,806.

Preferably the composition comprises one or more polysaccharides whichmay in particular be chosen from carboxymethyl cellulose,methylcarboxymethylcellulose, sulfoethylcellulose,methylhydroxyethylcellulose, carboxymethyl xyloglucan, carboxymethylxylan, sulfoethylgalactomannan, carboxymethyl galactomannan, hydoxyethylgalactomannan, sulfoethyl starch, carboxymethyl starch, and mixturethereof. Other polysaccharides suitable for use in the present inventionare the glucans. Preferred glucans are Poly alpha-1,3-glucan which is apolymer comprising glucose monomeric units linked together by glycosidiclinkages (i.e., glucosidic linkages), wherein at least about 50% of theglycosidic linkages are alpha-1,3-glycosidic linkages. Polyalpha-1,3-glucan is a type of polysaccharide. Poly alpha-1,3-glucan canbe enzymatically produced from sucrose using one or moreglucosyltransferase enzymes, such as described in U.S. Pat. No.7,000,000, and U.S. Patent Appl. Publ. Nos. 2013/0244288 and2013/0244287 (all of which are incorporated herein by reference), forexample.

Other suitable polysaccharides for use in the composition are cationicpolysaccharides. Examples of cationic polysaccharides include cationicguar gum derivatives, quaternary nitrogen-containing cellulose ethers,and synthetic polymers that are copolymers of etherified cellulose, guarand starch. When used, the cationic polymers herein are either solublein the composition or are soluble in a complex coacervate phase in thecomposition formed by the cationic polymer and the anionic, amphotericand/or zwitterionic surfactant component described hereinbefore.Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418;3,958,581; and U.S. Publication No. 2007/0207109A1.

Polymers can also function as deposition aids for other detergent rawmaterials. Preferred deposition aids are selected from the groupconsisting of cationic and nonionic polymers. Suitable polymers includecationic starches, cationic hydroxyethylcellulose,polyvinylformaldehyde, locust bean gum, mannans, xyloglucans, tamarindgum, polyethyleneterephthalate and polymers containingdimethylaminoethyl methacrylate, optionally with one or more monomersselected from the group comprising acrylic acid and acrylamide.

Additional Amines

Polyamines are known to improve grease removal. Preferred cyclic andlinear amines for performance are 1,3-bis (methylamine)-cyclohexane,4-methylcyclohexane-1,3-diamine (Baxxodur ECX 210 supplied by BASF) 1,3propane diamine, 1,6 hexane diamine,1,3 pentane diamine (Dytek EPsupplied by Invista), 2-methyl 1,5 pentane diamine (Dytek A supplied byInvista). U.S. Pat. No. 6,710,023 discloses hand dishwashingcompositions containing said diamines and polyamines containing at least3 protonable amines. Polyamines according to the invention have at leastone pka above the wash pH and at least two pka's greater than about 6and below the wash pH. Preferred polyamines with are selected from thegroup consisting of tetraethylenepentamine, hexaethylhexamine,heptaethylheptamines, octaethyloctamines, nonethylnonamines, andmixtures thereof commercially available from Dow, BASF and Huntman.Especially preferred polyetheramines are lipophilic modified asdescribed in U.S. Pat. Nos. 9,752,101, 9,487,739, 9,631,163

Dye Transfer Inhibitor (DTI)

The composition may comprise one or more dye transfer inhibiting agents.In one embodiment of the invention the inventors have surprisingly foundthat compositions comprising polymeric dye transfer inhibiting agents inaddition to the specified dye give improved performance. This issurprising because these polymers prevent dye deposition. Suitable dyetransfer inhibitors include, but are not limited to,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones andpolyvinylimidazoles or mixtures thereof. Suitable examples includePVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and ChromabondS-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, SokalanHP53, Sokalan HP59, Sokalan® HP 56K, Sokalan® HP 66 from BASF. Othersuitable DTIs are as described in WO2012/004134. When present in asubject composition, the dye transfer inhibiting agents may be presentat levels from about 0.0001% to about 10%, from about 0.01% to about 5%or even from about 0.1% to about 3% by weight of the composition.

Enzymes

Enzymes may be included in the cleaning compositions for a variety ofpurposes, including removal of protein-based, carbohydrate-based, ortriglyceride-based stains from substrates, for the prevention of refugeedye transfer in fabric laundering, and for fabric restoration. Suitableenzymes include proteases, amylases, lipases, carbohydrases, cellulases,oxidases, peroxidases, mannanases, and mixtures thereof of any suitableorigin, such as vegetable, animal, bacterial, fungal, and yeast origin.Other enzymes that may be used in the cleaning compositions describedherein include hemicellulases, peroxidases, proteases, cellulases,endoglucanases, xylanases, lipases, phospholipases, amylases,gluco-amylases, xylanases, esterases, cutinases, pectinases,keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases,or mixtures thereof, esterases, mannanases, pectate lyases, and ormixtures thereof. Other suitable enzymes include Nuclease enzyme. Thecomposition may comprise a nuclease enzyme. The nuclease enzyme is anenzyme capable of cleaving the phosphodiester bonds between thenucleotide sub-units of nucleic acids. The nuclease enzyme herein ispreferably a deoxyribonuclease or ribonuclease enzyme or a functionalfragment thereof. Enzyme selection is influenced by factors such aspH-activity and/or stability optima, thermostability, and stability toactive detergents, builders, and the like.

The enzymes may be incorporated into the cleaning composition at levelsfrom 0.0001% to 5% of active enzyme by weight of the cleaningcomposition. The enzymes can be added as a separate single ingredient oras mixtures of two or more enzymes.

In some embodiments, lipase may be used. Lipase may be purchased underthe trade name Lipex from Novozymes (Denmark). Amylases (Natalase®,Stainzyme®, Stainzyme Plus®) may be supplied by Novozymes, Bagsvaerd,Denmark. Proteases may be supplied by Genencor International, Palo Alto,Calif., USA (e.g. Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark(e.g. Liquanase®, Coronase®, Savinase®) . Other preferred enzymesinclude pectate lyases preferably those sold under the trade namesPectawash®, Xpect®, Pectaway® and the mannanases sold under the tradenames Mannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), andPurabrite® (Genencor International Inc., Palo Alto, California). A rangeof enzyme materials and means for their incorporation into syntheticcleaning compositions is disclosed in WO 9307263 A; WO 9307260 A; WO8908694 A; U.S. Pat. Nos. 3,553,139; 4,101,457; and 4,507,219. Enzymematerials useful for liquid cleaning compositions, and theirincorporation into such compositions, are disclosed in U.S. Pat. No.4,261,868.

Enzyme Stabilizing System

The enzyme-containing compositions described herein may optionallycomprise from about 0.001% to about 10%, in some examples from about0.005% to about 8%, and in other examples, from about 0.01% to about 6%,by weight of the composition, of an enzyme stabilizing system. Theenzyme stabilizing system can be any stabilizing system which iscompatible with the detersive enzyme. Such a system may be inherentlyprovided by other formulation actives, or be added separately, e.g., bythe formulator or by a manufacturer of detergent-ready enzymes. Suchstabilizing systems can, for example, comprise calcium ion, boric acid,propylene glycol, short chain carboxylic acids, boronic acids, chlorinebleach scavengers and mixtures thereof, and are designed to addressdifferent stabilization problems depending on the type and physical formof the cleaning composition. See U.S. Pat. No. 4,537,706 for a review ofborate stabilizers.

Chelating Agent.

Preferably the composition comprises chelating agents and/or crystalgrowth inhibitor. Suitable molecules include copper, iron and/ormanganese chelating agents and mixtures thereof. Suitable moleculesinclude aminocarboxylates, aminophosphonates, succinates, salts thereof,and mixtures thereof. Non-limiting examples of suitable chelants for useherein include ethylenediaminetetracetates,N-(hydroxyethyl)-ethylene-diamine-triacetates, nitrilotriacetates,ethylenediamine tetraproprionates, triethylene-tetraamine-hexacetates,diethylenetriamine-pentaacetates, ethanoldiglycines,ethylenediaminetetrakis (methylenephosphonates), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), ethylenediamine disuccinate(EDDS), hydroxyethanedimethylenephosphonic acid (HEDP),methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid(DTPA), and 1,2-diydroxybenzene-3,5-disulfonic acid (Tiron), saltsthereof, and mixtures thereof. Tiron as well as other sulphonatedcatechols may also be used as effective heavy metal chelants. Othernon-limiting examples of chelants of use in the present invention arefound in U.S. Pat. Nos. 7445644, 7585376 and 2009/0176684A1. Othersuitable chelating agents for use herein are the commercial DEQUESTseries, and chelants from Monsanto, DuPont, and Nalco Inc.

Brighteners

Optical brighteners or other brightening or whitening agents may beincorporated at levels of from about 0.01% to about 1.2%, by weight ofthe composition, into the cleaning compositions described herein.Commercial optical brighteners, which may be used herein, can beclassified into subgroups, which include, but are not necessarilylimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents. Examplesof such brighteners are disclosed in “The Production and Application ofFluorescent Brightening Agents,” M. Zahradnik, John Wiley & Sons, NewYork (1982). Specific, non-limiting examples of optical brightenerswhich may be useful in the present compositions are those identified inU.S. Pat. Nos. 4,790,856 and 3,646,015. Highly preferred Brightenersinclude Disodium4,4′-bis{[4-anilino-6-[bis(2-hydroxyethyl)amino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate,4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate,Disodium4,4″-bis[(4,6-di-anilino-s-triazin-2-yl)-amino]-2,2′-stilbenedisulfonateand disodium 4,4′-bis-(2-sulfostyryl)biphenyl.

Bleaching Agents.

It may be preferred for the composition to comprise one or morebleaching agents. Suitable bleaching agents include photobleaches,hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids andmixtures thereof.

(1) photobleaches for example sulfonated zinc phthalocyanine sulfonatedaluminium phthalocyanines, xanthene dyes and mixtures thereof;

(2) pre-formed peracids: Suitable preformed peracids include, but arenot limited to compounds selected from the group consisting ofpre-formed peroxyacids or salts thereof typically a percarboxylic acidsand salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, for example, Oxone®, and mixturesthereof. Suitable examples include peroxycarboxylic acids or saltsthereof, or peroxysulphonic acids or salts thereof. Particularlypreferred peroxyacids are phthalimido-peroxy-alkanoic acids, inparticular ε-phthalimido peroxy hexanoic acid (PAP). Preferably, theperoxyacid or salt thereof has a melting point in the range of from 30°C. to 60° C.

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof.

Fabric Shading Dyes

The fabric shading dye (sometimes referred to as hueing, bluing orwhitening agents) typically provides a blue or violet shade to fabric.Such dye(s) are well known in the art and may be used either alone or incombination to create a specific shade of hueing and/or to shadedifferent fabric types. The fabric shading dye may be selected from anychemical class of dye as known in the art, including but not limited toacridine, anthraquinone (including polycyclic quinones), azine, azo(e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), benzodifurane,benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine,diphenylmethane, formazan, hemicyanine, indigoids, methane,naphthalimides, naphthoquinone, nitro, nitroso, oxazine, phthalocyanine,pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenesand mixtures thereof. The amount of adjunct fabric shading dye presentin a laundry care composition of the invention is typically from 0.0001to 0.05 wt % based on the total cleaning composition, preferably from0.0001 to 0.005 wt %. Based on the wash liquor, the concentration offabric shading dye typically is from 1 ppb to 5 ppm, preferably from 10ppb to 500 ppb.

Suitable fabric shading dyes include small molecule dyes, polymeric dyesand dye-clay conjugates. Preferred fabric shading dyes are selected fromsmall molecule dyes and polymeric dyes. Suitable small molecule dyes maybe selected from the group consisting of dyes falling into the ColourIndex (C.I., Society of Dyers and Colourists, Bradford, UK)classifications of Acid, Direct, Basic, Reactive, Solvent or Dispersedyes.

Suitable polymeric dyes include dyes selected from the group consistingof polymers containing covalently bound (sometimes referred to asconjugated) chromogens, (also known as dye-polymer conjugates), forexample polymers with chromogen monomers co-polymerized into thebackbone of the polymer and mixtures thereof. Preferred polymeric dyescomprise the optionally substituted alkoxylated dyes, such asalkoxylated triphenyl-methane polymeric colourants, alkoxylatedcarbocyclic and alkoxylated heterocyclic azo colourants includingalkoxylated thiophene polymeric colourants, and mixtures thereof, suchas the fabric-substantive colorants sold under the name of Liquitint®(Milliken, Spartanburg, S.C., USA).

Suitable dye clay conjugates include dye clay conjugates selected fromthe group comprising at least one cationic/basic dye and a smectiteclay; a preferred clay may be selected from the group consisting ofMontmorillonite clay, Hectorite clay, Saponite clay and mixturesthereof.

Pigments are well known in the art and may also be used in the laundrycare compositions herein. Suitable pigments include C.I Pigment Blues 15to 20, especially 15 and/or 16, C.I. Pigment Blue 29, C.I. PigmentViolet 15, Monastral Blue and mixtures thereof.

Builders

The cleaning compositions of the present invention may optionallycomprise a builder. Builders selected from aluminosilicates andsilicates assist in controlling mineral hardness in wash water, or toassist in the removal of particulate soils from surfaces. Suitablebuilders may be selected from the group consisting of phosphatespolyphosphates, especially sodium salts thereof; carbonates,bicarbonates, sesquicarbonates, and carbonate minerals other than sodiumcarbonate or sesquicarbonate; organic mono-, di-, tri-, andtetracarboxylates, especially water-soluble non-surfactant carboxylatesin acid, sodium, potassium or alkanolammonium salt form, as well asoligomeric or water-soluble low molecular weight polymer carboxylatesincluding aliphatic and aromatic types; and phytic acid. These may becomplemented by borates, e.g., for pH-buffering purposes, or bysulfates, especially sodium sulfate and any other fillers or carrierswhich may be important to the engineering of stable surfactant and/orbuilder-containing cleaning compositions.

pH Buffer System

The compositions may also include a pH buffer system. The cleaningcompositions herein may be formulated such that, during use in aqueouscleaning operations, the wash water will have a pH of between about 6.0and about 12, and in some examples, between about 7.0 and 11. Techniquesfor controlling pH at recommended usage levels include the use ofbuffers, alkalis, or acids, and are well known to those skilled in theart. These include, but are not limited to, the use of sodium carbonate,citric acid or sodium citrate, monoethanol amine or other amines, boricacid or borates, and other pH-adjusting compounds well known in the art.The cleaning compositions herein may comprise dynamic in-wash pHprofiles by delaying the release of citric acid.

Structurant/Thickeners

Structured liquids can either be internally structured, whereby thestructure is formed by primary ingredients (e.g. surfactant material)and/or externally structured by providing a three dimensional matrixstructure using secondary ingredients (e.g. polymers, clay and/orsilicate material). The composition may comprise from about 0.01% toabout 5%, by weight of the composition, of a structurant, and in someexamples, from about 0.1% to about 2.0%, by weight of the composition,of a structurant. The structurant may be selected from the groupconsisting of diglycerides and triglycerides, ethylene glycoldistearate, microcrystalline cellulose, cellulose-based materials,microfiber cellulose, biopolymers, xanthan gum, gellan gum, and mixturesthereof. In some examples, a suitable structurant includes hydrogenatedcastor oil, and non-ethoxylated derivatives thereof. Other suitablestructurants are disclosed in U.S. Pat. No. 6,855,680. Such structurantshave a thread-like structuring system having a range of aspect ratios.Further suitable structurants and the processes for making them aredescribed in WO 2010/034736.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the cleaning compositions described herein. Sudssuppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos.4,489,455, 4,489,574, and in front-loading style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples ofsuds suppressors include monocarboxylic fatty acid, and soluble saltstherein, high molecular weight hydrocarbons such as paraffin, fatty acidesters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C18-C40 ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point belowabout 100° C., silicone suds suppressors, and secondary alcohols. Sudssuppressors are described in U.S. Pat. Nos. 2,954,347; 4,075,118;4,265,779; 4,265,779; 3,455,839; 3,933,672; 4,652,392; 4,978,471;4,983,316; 5,288,431; 4,639,489; 4,749,740; and 4,798,679.

The cleaning compositions herein may comprise from 0% to about 10%, byweight of the composition, of suds suppressor. When utilized as sudssuppressors, monocarboxylic fatty acids, and salts thereof, may bepresent in amounts up to about 5% by weight of the cleaning composition,and in some examples, may be from about 0.5% to about 3% by weight ofthe cleaning composition. Silicone suds suppressors may be utilized inamounts up to about 2.0% by weight of the cleaning composition, althoughhigher amounts may be used. Monostearyl phosphate suds suppressors maybe utilized in amounts ranging from about 0.1% to about 2% by weight ofthe cleaning composition. Hydrocarbon suds suppressors may be utilizedin amounts ranging from about 0.01% to about 5.0% by weight of thecleaning composition, although higher levels can be used. Alcohol sudssuppressors may be used at about 0.2% to about 3% by weight of thecleaning composition.

Suds Boosters

If high sudsing is desired, suds boosters such as the C10-C16alkanolamides may be incorporated into the cleaning compositions fromabout 1% to about 10% by weight of the cleaning composition. Someexamples include the C10-C14 monoethanol and diethanol amides. Ifdesired, water-soluble magnesium and/or calcium salts such as MgCl₂,MgSO₄, CaCl₂, CaSO₄, and the like, may be added at levels of about 0.1%to about 2% by weight of the cleaning composition, to provide additionalsuds and to enhance grease removal performance.

Fillers and Carriers

Fillers and carriers may be used in the cleaning compositions describedherein. As used herein, the terms “filler” and “carrier” have the samemeaning and can be used interchangeably. Liquid cleaning compositions,and other forms of cleaning compositions that include a liquid component(such as liquid-containing unit dose cleaning compositions), may containwater and other solvents as fillers or carriers. Low molecular weightprimary or secondary alcohols exemplified by methanol, ethanol,propanol, isopropanol, and phenoxyethanol are suitable. Monohydricalcohols may be used in some examples for solubilizing surfactants, andpolyols such as those containing from 2 to about 6 carbon atoms and from2 to about 6 hydroxy groups (e.g., 1,2-propanediol, 1,3-propanediol,2,3-butanediol, ethylene glycol, and glycerine may be used).Amine-containing solvents may also be used.

Methods of Use

The present invention includes methods for whitening fabric. Compactfluid detergent compositions that are suitable for sale to consumers aresuited for use in laundry pretreatment applications, laundry cleaningapplications, and home care applications. Such methods include, but arenot limited to, the steps of contacting detergent compositions in neatform or diluted in wash liquor, with at least a portion of a fabricwhich may or may not be soiled and then optionally rinsing the fabric.The fabric material may be subjected to a washing step prior to theoptional rinsing step. Machine laundry methods may comprise treatingsoiled laundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. An “effectiveamount” of the detergent composition means from about 20 g to about 300g of product dissolved or dispersed in a wash solution of volume fromabout 5 L to about 65 L. The water temperatures may range from about 5°C. to about 100° C. The water to soiled material (e.g., fabric) ratiomay be from about 1:1 to about 30:1. The compositions may be employed atconcentrations of from about 500 ppm to about 15,000 ppm in solution. Inthe context of a fabric laundry composition, usage levels may also varydepending not only on the type and severity of the soils and stains, butalso on the wash water temperature, the volume of wash water, and thetype of washing machine (e.g., top-loading, front-loading, vertical-axisJapanese-type automatic washing machine).

The detergent compositions herein may be used for laundering of fabricsat reduced wash temperatures. These methods of laundering fabriccomprise the steps of delivering a laundry detergent composition towater to form a wash liquor and adding a laundering fabric to said washliquor, wherein the wash liquor has a temperature of from about 0° C. toabout 20° C., or from about 0° C. to about 15° C., or from about 0° C.to about 9° C. The fabric may be contacted to the water prior to, orafter, or simultaneous with, contacting the laundry detergentcomposition with water. Another method includes contacting a nonwovensubstrate, which is impregnated with the detergent composition, with asoiled material. As used herein, “nonwoven substrate” can comprise anyconventionally fashioned nonwoven sheet or web having suitable basisweight, caliper (thickness), absorbency, and strength characteristics.Non-limiting examples of suitable commercially available nonwovensubstrates include those marketed under the trade names SONTARA® byDuPont and POLY WEB® by James River Corp.

Hand washing/soak methods, and combined hand washing with semi-automaticwashing machines, are also included.

Packaging for the Compositions

The cleaning compositions described herein can be packaged in anysuitable container including those constructed from paper, cardboard,plastic materials, and any suitable laminates. An optional packagingtype is described in European Application No. 94921505.7.

Multi-Compartment Pouch

The cleaning compositions described herein may also be packaged as amulti-compartment cleaning composition.

Other Adjunct Ingredients

A wide variety of other ingredients may be used in the cleaningcompositions herein, including, for example, other active ingredients,carriers, hydrotropes, processing aids, dyes or pigments, solvents forliquid formulations, solid or other liquid fillers, erythrosine,colliodal silica, waxes, probiotics, surfactin, aminocellulosicpolymers, Zinc Ricinoleate, perfume microcapsules, rhamnolipds,sophorolipids, glycopeptides, methyl ester ethoxylates, sulfonatedestolides, cleavable surfactants, biopolymers, silicones, modifiedsilicones, aminosilicones, deposition aids, hydrotropes (especiallycumene-sulfonate salts, toluene-sulfonate salts, xylene-sulfonate salts,and naphalene salts), PVA particle-encapsulated dyes or perfumes,pearlescent agents, effervescent agents, color change systems, siliconepolyurethanes, opacifiers, tablet disintegrants, biomass fillers,fast-dry silicones, glycol distearate, starch perfume encapsulates,emulsified oils including hydrocarbon oils, polyolefins, and fattyesters, bisphenol antioxidants, micro-fibrous cellulose structurants,properfumes, styrene/acrylate polymers, triazines, soaps, superoxidedismutase, benzophenone protease inhibitors, functionalized TiO2,dibutyl phosphate, silica perfume capsules, and other adjunctingredients, choline oxidase, triarylmethane blue and violet basic dyes,methine blue and violet basic dyes, anthraquinone blue and violet basicdyes, azo dyes basic blue 16, basic blue 65, basic blue 66 basic blue67, basic blue 71, basic blue 159, basic violet 19, basic violet 35,basic violet 38, basic violet 48, oxazine dyes, basic blue 3, basic blue75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, Nileblue A and xanthene dye basic violet 10, an alkoxylated triphenylmethanepolymeric colorant; an alkoxylated thiopene polymeric colorant;thiazolium dye, mica, titanium dioxide coated mica, bismuth oxychloride,and other actives.

Anti-oxidant: The composition may optionally contain an anti-oxidantpresent in the composition from about 0.001 to about 2% by weight.Preferably the antioxidant is present at a concentration in the range0.01 to 0.08% by weight. Mixtures of anti-oxidants may be used.

One class of anti-oxidants used in the present invention is alkylatedphenols. Hindered phenolic compounds are a preferred type of alkylatedphenols having this formula. A preferred hindered phenolic compound ofthis type is 3,5-di-tert-butyl-4-hydroxytoluene (BHT).

Furthermore, the anti-oxidant used in the composition may be selectedfrom the group consisting of α-, β-, γ-, δ-tocopherol, ethoxyquin,2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl hydroquinone,tert-butyl hydroxyanisole, lignosulphonic acid and salts thereof, andmixtures thereof.

The cleaning compositions described herein may also contain vitamins andamino acids such as: water soluble vitamins and their derivatives, watersoluble amino acids and their salts and/or derivatives, water insolubleamino acids viscosity modifiers, dyes, nonvolatile solvents or diluents(water soluble and insoluble), pearlescent aids, pediculocides, pHadjusting agents, preservatives, skin active agents, sunscreens, UVabsorbers, niacinamide, caffeine, and minoxidil.

The cleaning compositions of the present invention may also containpigment materials such as nitroso, monoazo, disazo, carotenoid,triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine,anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine,botanical, and natural colors, including water soluble components suchas those having C.I. Names.

The cleaning compositions of the present invention may also containantimicrobial agents. Cationic active ingredients may include but arenot limited to n-alkyl dimethyl benzyl ammonium chloride, alkyl dimethylethyl benzyl ammonium chloride, dialkyl dimethyl quaternary ammoniumcompounds such as didecyl dimethyl ammonium chloride,N,N-didecyl-Nmethyl-poly(oxyethyl) ammonium propionate, dioctyl didecylammonium chloride, also including quaternary species such asbenzethonium chloride and quaternary ammonium compounds with inorganicor organic counter ions such as bromine, carbonate or other moietiesincluding dialkyl dimethyl ammonium carbonates, as well as antimicrobialamines such as Chlorhexidine Gluconate, PHMB (Polyhexamethylenebiguanide), salt of a biguanide, a substituted biguanide derivative, anorganic salt of a quaternary ammonium containing compound or aninorganic salt of a quaternary ammonium containing compound or mixturesthereof.

In one aspect, such method comprises the steps of optionally washingand/or rinsing said surface or fabric, contacting said surface or fabricwith any composition disclosed in this specification then optionallywashing and/or rinsing said surface or fabric is disclosed, with anoptional drying step.

Drying of such surfaces or fabrics may be accomplished by any one of thecommon means employed either in domestic or industrial settings. Thefabric may comprise any fabric capable of being laundered in normalconsumer or institutional use conditions, and the invention is suitablefor cellulosic substrates and in some aspects also suitable forsynthetic textiles such as polyester and nylon and for treatment ofmixed fabrics and/or fibers comprising synthetic and cellulosic fabricsand/or fibers. As examples of synthetic fabrics are polyester, nylon,these may be present in mixtures with cellulosic fibers, for example,polycotton fabrics. The solution typically has a pH of from 7 to 11,more usually 8 to 10.5. The compositions are typically employed atconcentrations from 500 ppm to 5,000 ppm in solution. The watertemperatures typically range from about 5° C. to about 90° C. The waterto fabric ratio is typically from about 1:1 to about 30:1.

In a fifth embodiment, the invention provides a domestic method oftreating a textile material, the method comprising the steps of (a)treating the textile material with an aqueous solution of the leucopolymer, (b) optionally, rinsing the textile material, and (c)optionally, drying the textile material.

The leuco polymer used in the domestic treatment method can be any ofthe leuco polymers described above in connection with the earlierembodiments of the invention. The leuco polymer can be present in theaqueous solution in any suitable amount. In one aspect, the aqueoussolution comprises from about 10 ppb to about 5,000 ppm, preferablyabout 50 ppb to about 2 ppm, of the leuco polymer. In such anembodiment, the aqueous solution can further comprise a surfactant in anamount of from 0.0 g/L to about 6 g/L, preferably about 0.2 g/L to about4 g/L. Further, the aqueous solution utilized in the domestic treatmentmethod can be prepared by combining any of the laundry care compositionsdescribed above with a suitable amount of water. The domestic treatmentmethod can be performed in any suitable apparatus, such as a sink or adomestic clothes washing machine.

The following examples further illustrate the subject matter describedabove but, of course, should not be construed as in any way limiting thescope thereof.

EXAMPLES Preparation of Leuco Monomers

Leuco alcohol 3: A solution of 4,40-bis(dimethylamino)benzhydrol (1)(0.27 g, 1.0 mmol), 2-(methylphenylamino)ethanol (2) (0.18 g, 1.2 mmol),and p-toluenesulfonic acid (pTSA) monohydrate (0.76 g, 4 mmol) inmethanol (25 mL) is stirred at reflux with a Dean-Stark trap for 9 h.The mixture is diluted with methylene chloride and washed three timeswith aq. sodium bicarbonate. The organic layer is dried over anhydrousMgSO₄ and filtered. The filtrate is concentrated in vacuo to give aresidue which is purified by column chromatography on silica gel (1:1ethyl acetate/hexane) to yield the leuco alcohol intermediate 3.

Leuco Monomer 5: To a solution of intermediate 3 (0.12 g, 0.3 mmol) inmethylene chloride (30 mL) is added triethylamine (0.3 g, 3 mmol), anddimethylaminopyridine (0.011 g, 0.09 mmol). The mixture is stirred at 0°C. for 10 min under N2 atmosphere and methacryloyl chloride (4) (0.094g, 0.9 mmol) is then added dropwise. The resultant mixture is stirred atambient temperature for 24 h, after which it is concentrated in vacuo.The residue is purified by column chromatography on silica gel (2:3ethyl acetate/hexane) to give the desired leuco monomer 5.

CN-Substituted leuco alcohol 6: To a solution containing theaminoalcohol 3 (0.04 g, 0.1 mmol)in ethanol (0.1M) is added2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ, 0.34 g, 0.15 mmol). Themixture is stirred at reflux for 5 h. After the mixture is removed fromthe heat source, potassium cyanide (0.13 g, 2 mmol), dissolved in aminimum amount of water, is added. The mixture is stirred for 6 h,extracted four times with aq. sodium bicarbonate and washed withsaturated aq. sodium chloride. The organic layer is collected and driedover anhydrous MgSO₄. After filtration, the filtrate is concentrated togive a residue which is purified by column chromatography on silica gel(2:3 ethyl acetate/hexane) to give the desired product 6.

CN-Substituted leuco monomer 7: To a solution of intermediate 6 (0.03 g,0.07 mmol) in methylene chloride (15 mL) is added triethylamine (0.07 g,0.7 mmol), and dimethylaminopyridine (2.6 mg, 0.022 mmol). To thissolution is added dropwise methacryloyl chloride (4) (0.022 g, 0.21mmol) and the resultant mixture is stirred at room temperature for 24 h.Concentration in vacuo followed by purification via columnchromatography on silica gel (in 1:1 ethyl acetate/hexane) gives theleuco monomer 7.

Preparation of Leuco polymers

Leuco Polymer 9: A solution containing the monomer 5 (0.28 g, 0.6 mmol),methyl methacrylate 8 (MMA, 0.30 g, 3 mmol),2,2-azobis(isobutyronitrile) (AIBN; 0.006 g, 0.036 mmol), and DMF (2 mL)in an ampoule is subjected to repeated freeze-thaw cycles before theampoule is sealed under vacuum condition. The sealed ampoule is heatedat 70° C. for 18 h. The resultant solution is diluted 10-fold with THFand precipitated into excess hexane. The polymer precipitates arecollected, washed with methanol and dried to give Polymer 9.

Leuco Polymer 10: A solution containing the monomer 7 (0.86 g, 1.73mmol), MMA 8 (0.87 g, 8.65 mmol), AIBN (8.54 mg, 0.052 mmol), and1,4-dioxane (6 mL) in an ampoule is subjected to repeated freeze-thawcycles before the ampoule is sealed under vacuum condition. The sealedampoule is heated at 80° C. for 24 h. After polymerization, the solutionis diluted five-fold with 1,4-dioxane and precipitated into excesshexane. The precipitate is filtered, washed with methanol, and dried togive Polymer 10.

Test Methods

Fabric swatches used in the test methods herein are obtained fromTestfabrics, Inc. West Pittston, Pa., and are 100% Cotton, Style 403(cut to 2″×2″) and/or Style 464 (cut to 4″×6″), and an unbrightenedmultifiber fabric, specifically Style 41 (5 cm×10 cm).

All reflectance spectra and color measurements, including L*, a*, b*,K/S, and Whiteness Index (WI CIE) values on dry fabric swatches, aremade using one of four spectrophotometers: (1) a Konica-Minolta 3610dreflectance spectrophotometer (Konica Minolta Sensing Americas, Inc.,Ramsey, N.J., USA; D65 illumination, 10° observer, UV light excluded),(2) a LabScan XE reflectance spectrophotometer (HunterLabs, Reston, Va.;D65 illumination, 10° observer, UV light excluded), (3) a Color-Eye®7000A (GretagMacbeth, New Windsor, N.Y., USA; D65 light, UV excluded),or (4) a Color i7 spectrophotometer (X-rite, Inc., Grand Rapids, Mich.,USA; D65 light, UV excluded). Measurements are performed using twolayers of fabric, obtained by stacking smaller internal replicates(e.g., 2″×2″ Style 403) or folding of larger fabric swatches (e.g.,4″×6″ style 464).

Where fabrics are irradiated, unless otherwise indicated, the specifiedfabrics post-dry are exposed to simulated sunlight with irradiance of0.77 W/m² @ 420 nm in an Atlas Xenon Fade-Ometer Ci3000+ (Atlas MaterialTesting Technology, Mount Prospect, Ill., USA) equipped with Type SBorosilicate inner (Part no. 20277300) and outer (Part no. 20279600)filters, set at 37° C. maximum cabinet temperature, 57° C. maximum blackpanel temperature (BPT black panel geometry), and 35% RH (relativehumidity). Unless otherwise indicated, irradiation is continuous overthe stated duration.

I. Method for Determining Leuco Compound Efficiency from a Wash Solution

Cotton swatches (Style 403) are stripped prior to use by washing at 49°C. two times with heavy duty liquid laundry detergent nil brightener(1.55 g/L in aqueous solution). A concentrated stock solution of eachleuco compound to be tested is prepared in a solvent selected fromethanol or 50:50 ethanol:water, preferably ethanol.

A base wash solution is prepared by dissolving heavy duty liquid laundrydetergent nil brightener (5.23 g/1.0 L) in deionized water. Fourstripped cotton swatches are weighed together and placed in a 250 mLErlenmeyer flask along with two 10 mm glass marbles. A total of threesuch flasks are prepared for each wash solution to be tested. The basewash solution is dosed with the leuco colorant stock to achieve a washsolution with the desired 2.0×10⁻⁶ N wash concentration of the leucocolorant. (By way of example, a 1.0 ppm wash solution of a leucocolorant with equivalent weight of 493.65 g/equivalent, or a 1.5 ppmwash solution of a leuco colorant with equivalent weight of 757.97g/equivalent, provides a wash solution that is 2.0×10⁻⁶ N leuco.)

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburg, Pa.) and agitated at the maximum settingfor 12 minutes, after which the wash solution is removed by aspiration,a volume of rinse water (0 gpg) equivalent to the amount of washsolution used is added. Each flask is dosed with a 1000 gpg stockhardness solution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg)before agitating 4 more minutes. The rinse is removed by aspiration andthe fabric swatches are spun dry (Mini Countertop Spin Dryer, TheLaundry Alternative Inc., Nashua, N.H.) for 1 minute, then placed in afood dehydrator set at 135° F. to dry in the dark for 2 hours.

A. Dark Conditions Post-Dry

L*, a*, b* and Whiteness Index (WI CIE) values for the cotton fabricsare measured on the dry swatches 48 hours following the drying procedureusing a LabScan XE reflectance spectrophotometer. The L*, a*, and b*values of the 12 swatches generated for each leuco compound (threeflasks with four swatches each) are averaged and the leuco compoundefficiency (LCE) of each leuco compound is calculated using thefollowing equation:

LCE=DE*=[(L* _(c) −L* _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*_(s))²]^(1/2)

wherein the subscripts c and s respectively refer to the control, i.e.,the fabric washed in detergent with no leuco compound, and the sample,i.e., the fabric washed in detergent containing leuco compound.

The WI CIE values of the 12 swatches generated for each wash solution(three flasks with four swatches each) are averaged and the change inwhiteness index on washing is calculated using the following equation:

ΔWI=WI CIE (after wash)−WI CIE (before wash)

B. Light Conditions Post-Dry

Because consumer habits vary greatly throughout the world, the methodsused must allow for the possibility of measuring the benefits of leucocompounds across conditions. One such condition is the exposure to lightfollowing drying. Some leuco compounds will not exhibit as large abenefit under dark storage as under light storage, so each leucocompound must be tested under both sets of conditions to determine theoptimum benefit. Therefore Method I includes exposure of the driedfabrics to simulated sunlight for various increments of time beforemeasurements are taken, and the LCE value is set to the maximum valueobtained from the set of exposure times described below.

The specified cotton fabrics post-dry are exposed to simulated sunlightfor 15 min, 30 min, 45 min, 60 min, 75 min, 90 min, 120 min, and 240min. The L*, a*, b*, and Whiteness Index (WI CIE) values for the cottonfabrics are measured on the swatches after each exposure period using aLabScan XE reflectance spectrophotometer. The calculation of the LCE andthe OWI value at each exposure time point is as described in Method I.A.above, and the LCE value and the OWI value for the leuco compound areset to the maximum values obtained from the set of exposure timeslisted.

II. Method for Determining Relative Hue Angle (vs. Nil Leuco Compound)

The relative hue angle delivered by a leuco compound to cotton fabricstreated according to Method I described above is determined as follows.

-   -   a) The a* and b* values of the 12 swatches from each solution        are averaged and the following formulas used to determine Δa*        and Δb*:

Δa*=a* _(c) −a* _(s) and Δb*=b* _(c) −b* _(s)

-   -   -   wherein the subscripts c and s respectively refer to the            fabric washed in detergent with no leuco compound and the            fabric washed in detergent containing leuco compound.

    -   b) If the absolute value of both Δa* and Δb*<0.25, no Relative        Hue Angle (RHA) is calculated. If the absolute value of either        Δa* or Δb* is ≥0.25, the RHA is determined using one of the        following formulas:

RHA=A TAN 2(Δa*,Δb*) for Δb*≥0

RHA=360+A TAN 2(Δa*,Δb*) for Δb*<0

A relative hue angle can be calculated for each time point where data iscollected in either the dark post-dry or light post-dry assessments. Anyof these points may be used to satisfy the requirements of a claim.

III. Method for Determining Change in Whiteness Index for a Laundry CareFormulation

Cotton swatches (Style 403) are stripped prior to use by washing at 49°C. two times with heavy duty liquid laundry detergent nil brightener(1.55 g/L in aqueous solution).

A base wash solution is prepared by dissolving the laundry careformulation (5.23 g/1.0 L) in deionized water. Four stripped cottonswatches are weighed together and placed in a 250 mL Erlenmeyer flaskalong with two 10 mm glass marbles. A total of three such flasks areprepared.

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburg, Pa.) and agitated at the maximum settingfor 12 minutes, after which the wash solution is removed by aspiration,a volume of rinse water (0 gpg) equivalent to the amount of washsolution used is added. Each flask is dosed with a 1000 gpg stockhardness solution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg)before agitating 4 more minutes. The rinse is removed by aspiration andthe fabric swatches are spun dry (Mini Countertop Spin Dryer, TheLaundry Alternative Inc., Nashua, N.H.) for 1 minute, then placed in afood dehydrator set at 135° F. to dry in the dark for 2 hours.

L*, a*, b*, and Whiteness Index (WI CIE) values for the cotton fabricsare measured on the dry swatches, according to Method I.A. and/or I.B.above, using a LabScan XE reflectance spectrophotometer. The WI CIEvalues of the 12 swatches generated for the laundry care formulation(three flasks with four swatches each) are averaged and the change inwhiteness index on washing is calculated using the following equation:

ΔWI=WI CIE (after wash)−WI CIE (before wash)

FORMULATION EXAMPLES

The following are illustrative examples of cleaning compositionsaccording to the present disclosure and are not intended to be limiting.

Examples 1-7: Heavy Duty Liquid Laundry Detergent Compositions

1 2 3 4 5 6 7 Ingredients % weight AE_(1.8)S 6.77 5.16 1.36 1.30 — — —AE₃S — — — — 0.45 — — LAS 0.86 2.06 2.72 0.68 0.95 1.56 3.55 HSAS 1.852.63 1.02 — — — — AE9 6.32 9.85 10.20  7.92 AE8 35.45  AE7 8.40 12.44 C₁₂₋₁₄ dimethyl Amine Oxide 0.30 0.73 0.23 0.37 — — — C₁₂₋₁₈ Fatty Acid0.80 1.90 0.60 0.99 1.20 — 15.00  Citric Acid 2.50 3.96 1.88 1.98 0.902.50 0.60 Optical Brightener 1 1.00 0.80 0.10 0.30 0.05 0.50  0.001Optical Brightener 3 0.001 0.05 0.01 0.20 0.50 — 1.00 Sodium formate1.60 0.09 1.20 0.04 1.60 1.20 0.20 DTI 0.32 0.05 — 0.60 — 0.60 0.01Sodium hydroxide 2.30 3.80 1.70 1.90 1.70 2.50 2.30 Monoethanolamine1.40 1.49 1.00 0.70 — — — Diethylene glycol 5.50 — 4.10 — — — — Chelant1 0.15 0.15 0.11 0.07 0.50 0.11 0.80 4-formyl-phenylboronic acid — — — —0.05 0.02 0.01 Sodium tetraborate 1.43 1.50 1.10 0.75 — 1.07 — Ethanol1.54 1.77 1.15 0.89 — 3.00 7.00 Polymer 1 0.10 — — — — — 2.00 Polymer 20.30 0.33 0.23 0.17 — — — Polymer 3 — — — — — — 0.80 Polymer 4 0.80 0.810.60 0.40 1.00 1.00 — 1,2-Propanediol — 6.60 — 3.30 0.50 2.00 8.00Structurant 0.10 — — — — — 0.10 Perfume 1.60 1.10 1.00 0.80 0.90 1.501.60 Perfume encapsulate 0.10 0.05 0.01 0.02 0.10 0.05 0.10 Protease0.80 0.60 0.70 0.90 0.70 0.60 1.50 Mannanase 0.07 0.05 0.045 0.06 0.04 0.045 0.10 Amylase 1 0.30 — 0.30 0.10 — 0.40 0.10 Amylase 2 — 0.20 0.100.15 0.07 — 0.10 Xyloglucanase 0.20 0.10 — — 0.05 0.05 0.20 Lipase 0.400.20 0.30 0.10 0.20 — — Polishing enzyme — 0.04 — — —  0.004 — Nuclease0.05 — — — — —  0.003 Dispersin B — — — 0.05 0.03  0.001  0.001Liquitint ® V200 0.01 — — — — —  0.005 Leuco polymer 0.5 0.35 0.1 0.20.04 0.02 0.04 Dye control agent — 0.3 — 0.03 — 0.3 0.3  Water, dyes &minors Balance pH 8.2 Based on total cleaning and/or treatmentcomposition weight. Enzyme levels are reported as raw material.

Examples 8 to 18: Unit Dose Compositions

These examples provide various formulations for unit dose laundrydetergents. Compositions 8 to 12 comprise a single unit dosecompartment. The film used to encapsulate the compositions ispolyvinyl-alcohol-based film.

Ingredients 8 9 10 11 12 % weight LAS 19.09 16.76 8.59 6.56 3.44 AE3S1.91 0.74 0.18 0.46 0.07 AE7 14.00 17.50 26.33 28.08 31.59 Citric Acid0.6 0.6 0.6 0.6 0.6 C12-15 Fatty Acid 14.8 14.8 14.8 14.8 14.8 Polymer 34.0 4.0 4.0 4.0 4.0 Chelant 2 1.2 1.2 1.2 1.2 1.2 Optical Brightener 10.20 0.25 0.01 0.01 0.50 Optical Brightener 2 0.20 — 0.25 0.03 0.01Optical Brightener 3 0.18 0.09 0.30 0.01 — DTI 0.10 — 0.20 — — Glycerol6.1 6.1 6.1 6.1 6.1 Monoethanol amine 8.0 8.0 8.0 8.0 8.0Tri-isopropanol amine — — 2.0 — — Tri-ethanol amine — 2.0 — — — Cumenesulfonate — — — — 2.0 Protease 0.80 0.60 0.07 1.00 1.50 Mannanase 0.070.05 0.05 0.10 0.01 Amylase 1 0.20 0.11 0.30 0.50 0.05 Amylase 2 0.110.20 0.10 — 0.50 Polishing enzyme 0.005 0.05 — — — Nuclease 0.- 0.05 — —0.005 Dispersin B 0.010 0.05 0.005 0.005 — Cyclohexyl — — — 2.0 —dimethanol Leuco polymer 0.6 0.3 1.0 0.1 0.4 Liquitint ® V200 — — 0.010.05 — Structurant 0.14 0.14 0.14 0.14 0.14 Perfume 1.9 1.9 1.9 1.9 1.9Dye control agent 0.1 0.3 0.2 0.5 0.3 Water and To 100% miscellaneous pH7.5-8.2 Based on total cleaning and/or treatment composition weight.Enzyme levels are reported as raw material.

In the following examples the unit dose has three compartments, butsimilar compositions can be made with two, four or five compartments.The film used to encapsulate the compartments is polyvinyl alcohol.

Base compositions 13 14 15 16 Ingredients % weight HLAS 26.82 16.35 7.503.34 AE7 17.88 16.35 22.50 30.06 Citric Acid 0.5 0.7 0.6 0.5 C12-15Fatty acid 16.4 6.0 11.0 13.0 Polymer 1 2.9 0.1 — — Polymer 3 1.1 5.12.5 4.2 Cationic cellulose polymer — — 0.3 0.5 Polymer 6 — 1.5 0.3 0.2Chelant 2 1.1 2.0 0.6 1.5 Optical Brightener 1 0.20 0.25 0.01 0.005Optical Brightener 3 0.18 0.09 0.30 0.005 DTI 0.1 — 0.05 — Glycerol 5.35.0 5.0 4.2 Monoethanolamine 10.0 8.1 8.4 7.6 Polyethylene glycol — —2.5 3.0 Potassium sulfite 0.2 0.3 0.5 0.7 Protease 0.80 0.60 0.40 0.80Amylase 1 0.20 0.20 0.200 0.30 Polishing enzyme — — 0.005 0.005 Nuclease0.05 — — — Dispersin B — 0.010 0.010 0.010 MgCl₂ 0.2 0.2 0.1 0.3Structurant 0.2 0.1 0.2 0.2 Acid Violet 50 0.04 0.03 0.05 0.03Perfume/encapsulates 0.10 0.30 0.01 0.05 Dye control agent 0.2 0.03 0.4— Solvents and misc. To 100% pH 7.0-8.2 Finishing compositions 17 18Compartment A B C A B C Volume of each compartment 40 ml 5 ml 5 ml 40 ml5 ml 5 ml Ingredients Active material in Wt. % Perfume 1.6 1.6 1.6 1.61.6 1.6 Liquitint ® V200 0 0.006 0 0 0.004 — Leuco polymer 0.2 0.4 — —TiO2 — — 0.1 — 0.1 Sodium Sulfite 0.4 0.4 0.4 0.1 0.3 0.3 Polymer 5 — 2— — Hydrogenated castor oil 0.14 0.14 0.14 0.14 0.14 0.14 BaseComposition 13, 14, 15 Add to 100% or 16 Based on total cleaning and/ortreatment composition weight, enzyme levels are reported as rawmaterial.

-   AE1.8S is C₁₂₋₁₅ alkyl ethoxy (1.8) sulfate-   AE3S is C₁₂₋₁₅ alkyl ethoxy (3) sulfate-   AE7 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 7-   AE8 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 8-   AE9 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 9-   Amylase 1 is Stainzyme®, 15 mg active/g, supplied by Novozymes-   Amylase 2 is Natalase®, 29 mg active/g, supplied by Novozymes-   Xyloglucanase is Whitezyme®, 20 mg active/g, supplied by Novozymes-   Chelant 1 is diethylene triamine pentaacetic acid-   Chelant 2 is 1-hydroxyethane 1,1-diphosphonic acid-   Dispersin B is a glycoside hydrolase, reported as 1000 mg active/g-   DTI is either poly(4-vinylpyridine-1-oxide) (such as Chromabond    S-403E®), or poly(1-vinylpyrrolidone-co-1-vinylimidazole) (such as    Sokalan HP56®).-   Dye control agent Dye control agent in accordance with the    invention, for example Suparex® O.IN (M1), Nylofixan® P (M2),    Nylofixan® PM (M3), or Nylofixan® HF (M4)-   HSAS is mid-branched alkyl sulfate as disclosed in U.S. Pat. Nos.    6,020,303 and 6,060,443-   LAS is linear alkylbenzenesulfonate having an average aliphatic    carbon chain length C₉-C₁₅ (HLAS is acid form).-   Leuco colorant Any suitable leuco colorant or mixtures thereof    according to the instant invention.-   Lipase is Lipex®, 18 mg active/g, supplied by Novozymes-   Liquitint® V200 is a thiophene azo dye provided by Milliken-   Mannanase is Mannaway®, 25 mg active/g, supplied by Novozymes-   Nuclease is a Phosphodiesterase SEQ ID NO 1, reported as 1000 mg    active/g-   Optical Brightener 1 is disodium    4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate-   Optical Brightener 2 is disodium 4,4′-bis-(2-sulfostyryl)biphenyl    (sodium salt)-   Optical Brightener 3 is Optiblanc SPL10® from 3V Sigma-   Perfume encapsulate is a core-shell melamine formaldehyde perfume    microcapsules.-   Polishing enzyme is Para-nitrobenzyl esterase, reported as 1000 mg    active/g-   Polymer 1 is    bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)n),    wherein n=20-30, x=3 to 8 or sulphated or sulfonated variants    thereof-   Polymer 2 is ethoxylated (EO₁₅) tetraethylene pentamine-   Polymer 3 is ethoxylated polyethylenimine-   Polymer 4 is ethoxylated hexamethylene diamine-   Polymer 5 is Acusol 305, provided by Rohm&Haas-   Polymer 6 is a polyethylene glycol polymer grafted with vinyl    acetate side chains, provided by BASF.-   Protease is Purafect Prime®, 40.6 mg active/g, supplied by DuPont-   Structurant is Hydrogenated Castor Oil

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

We claim:
 1. A leuco polymer comprising a leuco monomer and an alkene,wherein the leuco polymer has a molecular weight of at least 500 and isobtainable by polymerization of the leuco monomer and one or more alkeneco-monomers, wherein the leuco monomer consists of an alkene covalentlybound to a leuco moiety and the leuco monomer has a maximum molarextinction coefficient at a wavelength in the range 400 to 750 nm ofless than 1000 M⁻¹cm⁻¹, wherein the alkene co-monomer(s) have a maximummolar extinction coefficient at a wavelength in the range 400 to 750 nmthat is less than 100 M⁻¹cm⁻¹.
 2. The leuco polymer of claim 1, whereinthe leuco moiety is selected from the group consisting of diarylmethaneleuco moieties, triarylmethane leuco moieties, oxazine moieties,thiazine moieties, hydroquinone moieties, and arylaminophenol moieties.3. The leuco polymer of claim 1, wherein the leuco monomer is of theform:

wherein Y is an organic bridging group covalently connecting a leucomoiety to the alkene moiety of the leuco monomer and R¹ is selected fromthe group consisting H, unsubstituted or substituted alkyl,unsubstituted or substituted aryl, benzyl, halogen, ester, acid amide,and cyano.
 4. The leuco polymer of claim 1, wherein the organic bridginggroup is selected from: —CON(R⁴)—, —CO₂—, —N(R⁴)—, —O—, —S—, —SO₂—,—SO₂N(R⁴)—, —N(COR⁴)—, and —N(SO₂R⁴)—; wherein R⁴ is selected from thegroup consisting of H, phenyl, benzyl and unsubstituted or substitutedC₁-C₆ branched or linear alkyl wherein the substituent of said linear orbranched alkyl is located between two carbons of said alkyl and isselected from the group consisting of —O—, —S—, —SO₂—, —CO₂—, and anamine.
 5. The leuco polymer of claim 4, wherein the organic bridginggroup is —CON(R⁴)—.
 6. The leuco polymer of claim 5, wherein R⁴ isselected from H and methyl.
 7. The leuco polymer of claim 3, wherein theY group is bound directly to a carbon atom of an aromatic ring of theleuco moiety.
 8. The leuco polymer of claim 3, wherein R¹ is selectedfrom H, methyl, ethyl, propyl, CO₂C₁₋₄ branched and linear alkyl chains,phenyl, benzyl, CN, Cl, and F.
 9. The leuco polymer of claim 3, whereinR¹ is selected from H and methyl.
 10. The leuco polymer of claim 4,wherein the leuco monomer is selected from the group consisting of: (i)a leuco moiety wherein one —NR⁴H of the leuco moiety is converted to—NR⁴—C(O)—CH═CH₂ or —NR⁴—C(O)—C(Me)═CH₂, wherein R⁴is as defined above;or (ii) a leuco moiety wherein one —OH of the leuco moiety is convertedto —O—C(O)—CH═CH₂ or —O—C(O)—C(Me)═CH₂.
 11. The leuco polymer of claim10, wherein the leuco monomer is:

wherein the leuco moiety carries at least one sulphonate.
 12. The leucopolymer of claim 10, wherein the leuco monomer is:

wherein the leuco moiety carries at least one sulphonate.
 13. The leucopolymer of claim 1, wherein the co-monomer is selected from:

wherein R² and R³ are independently selected from H, C₁-C₈ branched,cyclic and linear alkyl chains, C(O)OH, CO₂C₁₋₁₈ branched and linearalkyl chains, —C(O)N(C₁₋₁₈)₂, —C(O)N(C₁₋₁₈)H, —C(O)NH₂, andheteroaromatic, phenyl, benzyl, polyether, cyano, Cl and F.
 14. Theleuco polymer of claim 13, wherein R² and R³ of the co-monomer isfurther substituted by groups selected from charged and unchargedorganic, the further groups having a total molecular weight of less than400.
 15. The leuco polymer of claim 2, wherein the leuco moiety is aunivalent or polyvalent moiety derived by removal of one or morehydrogen atoms from a structure of Formula (I), (II), (III), (IV), or(V) . . .

wherein the ratio of Formula I-V to its oxidized form is at least 1:3;wherein each individual R_(o), R_(m) and R_(p) group on each of rings A,B and C is independently selected from the group consisting of hydrogen,deuterium and R⁵; wherein each R⁵ is independently selected from thegroup consisting of halogens, nitro, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, —C(O)R¹, —C(O)OR¹,—C(O)O⁻, —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹,—S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR²,—NR¹C(O)NR²R³, —OR¹, —NR¹R², —P(O)₂R¹, —P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and—P(O)(O⁻)₂; wherein at least one of the R_(o) and R_(m) groups on atleast one of the three rings A, B or C is hydrogen; each R_(p) isindependently selected from hydrogen, —OR¹ and —NR¹R²; wherein G isindependently selected from the group consisting of hydrogen, deuterium,C₁-C₁₆ alkoxide, phenoxide, bisphenoxide, nitrite, nitrile, alkyl amine,imidazole, arylamine, polyalkylene oxide, halides, alkylsulfide, arylsulfide, and phosphine oxide; wherein R¹, R² and R³ are independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, alkaryl, substituted alkaryl, and R⁴; R⁴is a organic group composed of one or more organic monomers with saidmonomer molecular weights ranging from 28 to 500; wherein e and f areindependently integers from 0 to 4; wherein each R²⁰ and R²¹ isindependently selected from the group consisting of a halogen, a nitrogroup, alkyl groups, substituted alkyl groups, —NC(O)OR¹, —NC(O)SR¹,—OR¹, and —NR¹R²; wherein each R²⁵ is independently selected from thegroup consisting of a monosaccharide moiety, a disaccharide moiety, anoligosaccharide moiety, a polysaccharide moiety, —C(O)R¹, —C(O)OR¹,—C(O)NR¹R²; wherein each R²² and R²³ is independently selected from thegroup consisting of hydrogen, an alkyl group, and substituted alkylgroups; wherein R³⁰ is positioned ortho or para to the bridging aminemoiety and is selected from the group consisting of —OR³⁸ and —NR³⁶R³⁷,wherein each R³⁶ and R³⁷ is independently selected from the groupconsisting of hydrogen, an alkyl group, a substituted alkyl group, anaryl group, a substituted aryl group, an acyl group, R⁴, —C(O)OR¹,—C(O)R¹, and —C(O)NR¹R²; wherein R³⁸ is selected from the groupconsisting of hydrogen, an acyl group, —C(O)OR¹, —C(O)R¹, and—C(O)NR¹R²; wherein g and h are independently integers from 0 to 4;wherein each R³¹ and R³² is independently selected from the groupconsisting of an alkyl group, a substituted alkyl group, an aryl group,a substituted aryl group, an alkaryl, substituted alkaryl, —C(O)R¹,—C(O)OR¹, —C(O)O⁻, —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R²,—S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR²,—NR¹C(O)SR², —NR¹C(O)NR²R³, —OR¹, —NR¹R², —P(O)₂R¹, —P(O)(OR¹)₂,—P(O)(OR¹)O⁻, and —P(O)(O⁻)₂; wherein —NR³⁴R³⁵ is positioned ortho orpara to the bridging amine moiety and R³⁴ and R³⁵ are independentlyselected from the group consisting of hydrogen, an alkyl, a substitutedalkyl, an aryl, a substituted aryl, an alkaryl, a substituted alkaryl,and R⁴; wherein R³³ is independently selected from the group consistingof hydrogen, —S(O)₂R¹, —C(O)N(H)R¹; —C(O)OR¹; and —C(O)R¹; wherein wheng is 2 to 4, any two adjacent R³¹ groups may combine to form a fusedring of five or more members wherein no more than two of the atoms inthe fused ring may be nitrogen atoms; wherein X⁴⁰ is selected from thegroup consisting of an oxygen atom, a sulfur atom, and NR⁴⁵; wherein R⁴⁵is independently selected from the group consisting of hydrogen,deuterium, an alkyl, a substituted alkyl, an aryl, a substituted aryl,an alkaryl, a substituted alkaryl, —S(O)₂OH, —S(O)₂O⁻, —C(O)OR¹,—C(O)R¹, and —C(O)NR¹R²; wherein R⁴⁰ and R⁴¹ are independently selectedfrom the group consisting of —OR¹ and —NR¹R²; wherein j and k areindependently integers from 0 to 3; wherein R⁴² and R⁴³ areindependently selected from the group consisting of an alkyl, asubstituted alkyl, an aryl, a substituted aryl, an alkaryl, asubstituted alkaryl, —S(O)₂R¹, —C(O)NR¹R², —NC(O)OR¹, —NC(O)SR¹,—C(O)OR¹, —C(O)R¹, —OR¹, —NR¹R²; wherein R⁴⁴ is —C(O)R¹, —C(O)NR¹R², and—C(O)OR¹; wherein any charge present in any of the compounds is balancedwith a suitable independently selected internal or external counterion.16. The leuco polymer of claim 15, wherein the leuco moiety is aunivalent or polyvalent moiety derived by removal of one or morehydrogen atoms from a compound conforming to a structure of Formula (I),(II), or (IV).
 17. The leuco polymer of claim 15, wherein the leucomoiety is a moiety of Formula (I).
 18. The leuco polymer of claim 16,wherein two R_(o) groups on different A, B and C rings combine to form afused ring of five or more members.
 19. The leuco polymer of claim 18,wherein the fused ring is six or more members and two R_(o) groups ondifferent A, B and C rings combine to form an organic linker containingone or more heteroatoms.
 20. The leuco polymer of claim 19, wherein twoR_(o) on different A, B and C rings combine to form a heteroatom bridgeselected from —0—and —S—to create a six member fused ring.
 21. The leucopolymer of claim 17, wherein either an R_(o) and R_(m) on the same ringor an R_(m) and R_(p) on the same ring combine to form a fused aliphaticring or fused aromatic ring.
 22. The leuco polymer of claim 17, whereinall four of the R_(o) and R_(m) groups on at least one of the threerings A, B or C are hydrogen.
 23. The leuco polymer of claim 22, whereinall of the R_(o) and R_(m) groups on all three rings A, B or C arehydrogen.
 24. The leuco polymer of claim 17, wherein all three R_(p) are—NR¹R².
 25. The leuco polymer of claim 1, wherein the leuco polymerfurther comprises a covalently bound chromophore moiety, wherein thechromophore moiety is selected from the group consisting ofdiarylmethane moieties, triarylmethane moieties, oxazine moieties,thiazine moieties, anthraquinone moieties, and indoaniline moieties.